CN117001994A - 3D printing of sealing caps - Google Patents

3D printing of sealing caps Download PDF

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Publication number
CN117001994A
CN117001994A CN202310969034.0A CN202310969034A CN117001994A CN 117001994 A CN117001994 A CN 117001994A CN 202310969034 A CN202310969034 A CN 202310969034A CN 117001994 A CN117001994 A CN 117001994A
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CN
China
Prior art keywords
reactive composition
reactive
fastener
sealing
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202310969034.0A
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Chinese (zh)
Inventor
B·W·维尔金森
M·A·布巴斯
林仁和
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PPG Industries Ohio Inc
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PPG Industries Ohio Inc
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Publication date
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Publication of CN117001994A publication Critical patent/CN117001994A/en
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/30—Auxiliary operations or equipment
    • B29C64/307—Handling of material to be used in additive manufacturing
    • B29C64/314—Preparation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/68—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts by incorporating or moulding on preformed parts, e.g. inserts or layers, e.g. foam blocks
    • B29C70/74—Moulding material on a relatively small portion of the preformed part, e.g. outsert moulding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D99/00—Subject matter not provided for in other groups of this subclass
    • B29D99/0053—Producing sealings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
    • B33Y40/20—Post-treatment, e.g. curing, coating or polishing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16B—DEVICES FOR FASTENING OR SECURING CONSTRUCTIONAL ELEMENTS OR MACHINE PARTS TOGETHER, e.g. NAILS, BOLTS, CIRCLIPS, CLAMPS, CLIPS OR WEDGES; JOINTS OR JOINTING
    • F16B33/00—Features common to bolt and nut
    • F16B33/004—Sealing; Insulation
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16B—DEVICES FOR FASTENING OR SECURING CONSTRUCTIONAL ELEMENTS OR MACHINE PARTS TOGETHER, e.g. NAILS, BOLTS, CIRCLIPS, CLAMPS, CLIPS OR WEDGES; JOINTS OR JOINTING
    • F16B37/00—Nuts or like thread-engaging members
    • F16B37/14—Cap nuts; Nut caps or bolt caps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2081/00—Use of polymers having sulfur, with or without nitrogen, oxygen or carbon only, in the main chain, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/26—Sealing devices, e.g. packaging for pistons or pipe joints

Abstract

A method of manufacturing a sealing cap using three-dimensional printing is disclosed. The sealing cap is used for sealing the fastener.

Description

3D printing of sealing caps
The application is a divisional application of a Chinese patent application with the application number of 202080024807.2.
The present application claims the benefit of U.S. c. ≡119 (e) U.S. provisional application No. 62/803,682, filed on 11, 2, 2019, which is incorporated by reference in its entirety.
Technical Field
The present disclosure relates to sealing fasteners, methods of manufacturing sealing caps, and sealing caps manufactured according to such methods.
Background
The sealing cap is used to seal and protect the fastener from environmental conditions. Depending on the application, it may be desirable for the sealing cap to exhibit one or more properties including chemical resistance, corrosion resistance, hydrolytic stability, low temperature flexibility, high temperature resistance, and the ability to dissipate electrical charges. Fasteners such as rivets, bolts, screws, nuts, anchors, washers, and the like of various shapes and sizes are used to secure the parts and may extend to varying degrees onto the surface. It is useful to have a sealing cap that optimizes materials and dimensions for a particular application.
Disclosure of Invention
According to the application, a method of sealing a fastener includes depositing a continuous layer including a first co-reactive composition directly onto the fastener by three-dimensional printing.
According to the invention, a method of manufacturing a sealing cap comprises depositing successive layers of a first co-reactive composition by three-dimensional printing to form a sealing cap shell defining an interior volume; and filling the interior volume with a second co-reactive composition to provide a sealing cap.
Sealing caps and sealing fasteners made according to the present method are also within the scope of the invention.
Drawings
The drawings described herein are for illustration purposes only. The drawings are not intended to limit the scope of the present disclosure.
FIGS. 1A-1B show cross-sectional views of a seal cap assembled over a fastener.
Figures 2A-2C show a perspective view of the exterior of the seal cap, a cross-sectional view of the seal cap, and a cross-sectional view of the co-reactive composition with the interior volume of the filled shell, respectively.
Fig. 3A-3C show photographs of polyurea sealing caps made according to the methods provided by the present disclosure.
Fig. 3D shows confocal laser scanning microscopy surface profiles (10X) of the corresponding sealing caps shown in fig. 3A-3C.
Fig. 4 shows a photograph of a sealing cap made according to example 4.
Detailed Description
For purposes of the following detailed description, it is to be understood that the embodiments provided by the present disclosure may assume various alternative variations and step sequences, except where expressly specified to the contrary. Furthermore, all numbers expressing, for example, quantities of ingredients used in the specification and claims, other than in any operating example, or unless otherwise indicated, are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.
Moreover, it should be understood that any numerical range recited herein is intended to include all sub-ranges subsumed therein. For example, a range of "1 to 10" is intended to include all subranges between the minimum value of 1 (inclusive) and the maximum value of 10 (inclusive), i.e., a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10.
"alkanediyl" means a diradical of a saturated, branched or straight chain acyclic hydrocarbon group having, for example, from 1 to 18 carbon atoms (C 1-18 ) From 1 to 14 carbon atoms (C 1-14 ) Of 1 to 6 carbon atoms (C 1-6 ) Of 1 to 4 carbon atoms (C 1-4 ) Or 1 to 3 hydrocarbon atoms (C) 1-3 ). The alkanediyl group may be C 2-14 Alkanediyl, C 2-10 AlkanesDiradical, C 2-8 Alkanediyl, C 2-6 Alkanediyl, C 2-4 Alkanediyl or C 2-3 Alkanediyl. Examples of alkanediyl groups include methane-diyl (-CH) 2 (-), ethane-1, 2-diyl (-CH) 2 CH 2 (-), propane-1, 3-diyl and isopropane-1, 2-diyl (e.g., -CH) 2 CH 2 CH 2 -and-CH (CH) 3 )CH 2 (-), butane-1, 4-diyl (-CH) 2 CH 2 CH 2 CH 2 (-), pentane-1, 5-diyl (-CH) 2 CH 2 CH 2 CH 2 CH 2 (-), hexane-1, 6-diyl (-CH) 2 CH 2 CH 2 CH 2 CH 2 CH 2 -), heptane-1, 7-diyl, octane-1, 8-diyl, nonane-1, 9-diyl, decane-1, 10-diyl and dodecane-1, 12-diyl.
"alkane cycloalkane" refers to a saturated hydrocarbon group having one or more cycloalkyl and/or cycloalkanediyl groups and one or more alkyl and/or alkanediyl groups, wherein cycloalkyl, cycloalkanediyl, alkyl and alkanediyl are as defined herein. Each cycloalkyl and/or cycloalkanediyl group may be C 3-6 、C 5-6 A cyclohexyl group or a cyclohexanediyl group. Each alkyl and/or alkanediyl group can be, for example, C 1-6 、C 1-4 、C 1-3 Methyl, methane diyl, ethyl or ethane-1, 2-diyl. The alkane-cycloalkane group may be, for example, C 4-18 Alkane cycloalkane, C 4-16 Alkane cycloalkane, C 4-12 Alkane cycloalkane, C 4-8 Alkane cycloalkane, C 6-12 Alkane cycloalkane, C 6-10 Alkane cycloalkanes or C 6-9 Alkane cycloalkanes. Examples of alkane-cycloalkane groups include 1, 3-tetramethyl cyclohexane and cyclohexyl methane.
"alkane cycloalkanediyl" refers to a diradical of an alkane cycloalkane radical. The alkanecycloalkanediyl radical may be, for example, C 4-18 Alkanecycloalkanediyl, C 4-16 Alkanecycloalkanediyl, C 4-12 Alkanecycloalkanediyl, C 4-8 Alkanecycloalkanediyl, C 6-12 Alkanecycloalkanediyl, C 6-10 Alkane cycloalkanesHydrocarbadiyl or C 6-9 Alkane cycloalkanediyl. Examples of alkane cycloalkanediyl groups include 1, 3-tetramethyl cyclohexane-1, 5-diyl and cyclohexylmethane-4, 4' -diyl.
"alkane arene" refers to a hydrocarbon group having one or more aryl and/or arene diyl groups and one or more alkyl and/or alkane diyl groups, wherein aryl, arene diyl, alkyl, and alkane diyl are defined herein. Each aryl and/or aryldiyl group may be C 6-12 、C 6-10 Phenyl or phenyldiyl. Each alkyl and/or alkanediyl group may be C 1-6 、C 1-4 、C 1-3 Methyl, methane diyl, ethyl or ethane-1, 2-diyl. The alkane-arene group may be C 6-18 Alkane arene, C 6-16 Alkane arene, C 6-12 Alkane arene, C 6-8 Alkane arene, C 6-12 Alkane arene, C 6-10 Alkane aromatics or C 6-9 Alkane arene. Examples of paraffinic aromatic groups include diphenylmethane.
"alkane arene diradical" refers to a diradical of an alkane arene group. The alkylarylanediyl group can be, for example, C 6-18 Alkanearene diradical, C 6-16 Alkanearene diradical, C 6-12 Alkanearene diradical, C 6-8 Alkanearene diradical, C 6-12 Alkanearene diradical, C 6-10 Alkanearene diyl or C 6-9 Alkane arene diradicals. Examples of alkane arene diyl groups include diphenylmethane-4, 4' -diyl.
"alkenyl" group refers to the structure-cr=c (R) 2 Wherein the alkenyl group is one group and is bonded to a larger molecule. In such embodiments, each R may independently comprise, for example, hydrogen and C 1-3 An alkyl group. Each R may be hydrogen and the alkenyl group may have the structure-ch=ch 2 。
"alkoxy" refers to an-OR group, wherein R is alkyl as defined herein. Examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy and n-butoxy. The alkoxy group may be C 1-8 Alkoxy, C 1-6 Alkoxy, C 1-4 Alkoxy or C 1-3 An alkoxy group.
"alkyl" refers to a single radical of a saturated, branched, or straight chain acyclic hydrocarbon group having, for example, 1 to 20 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms, 1 to 4 carbon atoms, or 1 to 3 carbon atoms. The alkyl group may be, for example, C 1-6 Alkyl, C 1-4 Alkyl or C 1-3 An alkyl group. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-hexyl, n-decyl and tetradecyl. The alkyl group may be, for example, C 1-6 Alkyl, C 1-4 Alkyl and C 1-3 An alkyl group.
"aromatic hydrocarbon diradicals" refer to diradicals of monocyclic or polycyclic aromatic groups. Examples of arene diyl groups include benzene diyl and naphthalene diyl. The arene-diyl group may be, for example, C 6-12 Aromatic diyl, C 6-10 Aromatic diyl, C 6-9 Aromatic hydrocarbon diradicals or benzene diradicals.
"cycloalkanediyl" refers to a diradical saturated monocyclic or polycyclic hydrocarbon group. The cycloalkanediyl group may be, for example, C 3-12 Cycloalkanediyl, C 3-8 Cycloalkanediyl, C 3-6 Cycloalkanediyl or C 5-6 Cycloalkanediyl groups. Examples of cycloalkanediyl groups include cyclohexane-1, 4-diyl, cyclohexane-1, 3-diyl and cyclohexane-1, 2-diyl.
"cycloalkyl" refers to a saturated monocyclic or polycyclic hydrocarbon mono-radical group. Cycloalkyl groups can be, for example, C 3-12 Cycloalkyl, C 3-8 Cycloalkyl, C 3-6 Cycloalkyl or C 5-6 Cycloalkyl groups.
"Heteroalkanediyl" refers to an alkanediyl group in which one or more carbon atoms are replaced by heteroatoms such as N, O, S or P. In the heteroalkanediyl group, one or more heteroatoms may be N or O.
"Heterocycloalkanediyl" refers to a cycloalkanediyl in which one or more carbon atoms are replaced by heteroatoms such as N, O, S or P. In the heterocycloalkyl diradical, one or more heteroatoms may be N or O.
"backbone" of the prepolymer refers to the reactive functionalitySegments between the clusters. The prepolymer backbone typically comprises repeating subunits. For example, polythiols HS- [ R ]] n The backbone of-SH is- [ R ]] n –。
"coreactive composition" refers to a composition comprising two or more coreactive compounds capable of reacting at a temperature of, for example, less than 50 ℃, less than 40 ℃, less than 30 ℃, or less than 20 ℃. The reaction between two or more compounds may be initiated by combining and mixing two or more co-reactive compounds and/or by exposing a co-reactive composition comprising two or more co-reactive compounds to a suitable catalyst or a suitable activated polymerization initiator, such as a photopolymerization initiator exposed to actinic radiation. Suitable catalysts and suitable polymerization initiators are capable of accelerating or initiating a chemical reaction between the co-reactive compounds. The catalyst may be a latent catalyst that can be activated by exposure to energy such as heat, actinic radiation, or mechanical forces such as shear forces. For example, the co-reactive composition may be formed by combining and mixing a first reactive component comprising a first reactive compound with a second reactive component comprising a second reactive compound, wherein the first reactive compound may react with the second reactive compound.
The "core" of a compound or polymer refers to the segment between reactive functional groups. For example, the core of polythiol HS-R-SH is-R-. The core of the compound or prepolymer may also be referred to as the backbone of the compound or the backbone of the prepolymer. The core of the polyfunctionalizing agent may be an atom or structure such as a cycloalkane, a substituted cycloalkane, a heterocycloalkyl, a substituted heterocycloalkyl, an arene, a substituted arene, a heteroarene, or a substituted heteroarene from which the moiety having the reactive functional group is bound.
"cure time" refers to the duration of time from when the curing reaction of the co-reactive composition is first initiated, e.g., by combining and mixing the co-reactive components to form the co-reactive composition and/or by exposing the co-reactive composition to actinic radiation, to when a layer prepared from the co-reactive composition exhibits a shore hardness of 30A at 25 ℃ and 50% RH. For an actinic radiation curable composition, the cure time refers to the duration from the first exposure of the coreactant composition to actinic radiation until a layer prepared from the exposed coreactant composition exhibits a shore hardness of 30A at 25 ℃ and 50% RH.
During curing, the co-reactive composition may be characterized by a working time, a tack free time, a cure onset, and a complete cure. The working time or gel time refers to the time from when the reaction between the ingredients is initiated, for example by mixing and/or activating the polymerization initiator, to when the co-reactive composition can no longer be stirred by hand. Tack free time refers to the time from the reaction between the first initiating components to the time the surface of the cured coreactive composition is no longer tack free. The cure onset time refers to the time from the reaction between the initiating components to the curing of the coreactive composition to produce a measurable hardness. The complete cure time may refer to the time for the cured composition to reach a hardness within 90% of the maximum hardness. These times may vary significantly depending on, for example, the ingredients of the co-reactive composition, the cure chemistry, the temperature, the catalyst, the cure accelerator, and/or the presence of the photopolymerization initiator.
A dash ("-") that is not between two letters or symbols is used to indicate a substituent or a bonding point between two atoms. For example, -CONH 2 Through a carbon atom.
"derived from" as in "moiety derived from a compound" refers to the moiety that is generated when the parent compound reacts with the reactant. For example, bis (alkenyl) compounds CH 2 ＝CH–R–CH＝CH 2 Can be reacted with another compound such as a compound having a thiol group to produce a moiety- (CH) 2 ) 2 –R–(CH 2 ) 2 -, derived from the reaction of an alkenyl group with a thiol group. As another example, for a parent diisocyanate having the structure o=c=n-R-n=c=o, the moiety derived from the diisocyanate has the structure-C (O) -NH-R-NH-C (O) -.
"derived from the reaction of-V with a thiol" refers to the moiety-V' -, which results from the reaction of a thiol group with a moiety comprising a functional group that is reactive with a thiol group. Example(s)For example, the group V-may include CH 2 ＝CH–CH 2 -O-, wherein the alkenyl group CH 2 =ch-can react with thiol group-SH. When reacted with thiol groups, part of-V' -is-CH 2 –CH 2 –CH 2 –O–。
Glass transition temperature T g Determined by Dynamic Mechanical Analysis (DMA) using a TA Instruments Q800 device (frequency 1Hz, amplitude 20 microns, and temperature ramp-80 ℃ C. To 25 ℃ C.), where T g Identified as the peak of the tan delta curve.
Monomers refer to low molecular weight compounds and may have a molecular weight of, for example, less than 1,000Da, less than 800Da, less than 600Da, less than 500Da, less than 400Da, or less than 300 Da. The monomer may have a molecular weight of, for example, 100Da to 1,000Da, 100Da to 800Da, 100Da to 600Da, 150Da to 550Da, or 200Da to 500 Da. The monomer may have a molecular weight of greater than 100Da, greater than 200Da, greater than 300Da, greater than 400Da, greater than 500Da, greater than 600Da, or greater than 800 Da. The monomer may have two or more reactive functionalities, such as 2 to 6, 2 to 5, or 2 to 4. The monomer can have a functionality of 2, 3, 4, 5, 6, or a combination of any of the foregoing. The monomers may have an average reactive functionality of, for example, 2 to 6, 2 to 5, 2 to 4, 2 to 3, 2.1 to 2.8, or 2.2 to 2.6. Reactive functionality refers to the number of reactive groups per molecule. Combinations of compounds having different reactive functionalities can be characterized by average non-integer reactive functionalities.
"polyalkenyl" refers to a compound having at least two alkenyl groups. At least two alkenyl groups may be terminal alkenyl groups, and such polyalkenyl groups may be referred to as alkenyl-terminated compounds. The alkenyl group may also be a pendant alkenyl group. The polyalkenyl group may be a dienyl group having two alkenyl groups. The polyalkenyl group may have more than two alkenyl groups, for example three to six alkenyl groups. The polyalkenyl groups may comprise a single type of polyalkenyl group, may be a combination of polyalkenyl groups having the same alkenyl functionality, or may be a combination of polyalkenyl groups having different alkenyl functionalities.
"prepolymer" refers to homopolymers and copolymers. For thiol-terminated prepolymers, the molecular weight is the number average molecular weight "Mn" as determined by end group analysis using iodine titration. For non-thiol-terminated prepolymers, the number average molecular weight is determined by gel permeation chromatography using polystyrene standards. The prepolymer includes a backbone and reactive functional groups capable of reacting with another compound, such as a curing agent or cross-linking agent, to form a cured polymer. The prepolymer comprises a plurality of repeating subunits, which may be the same or different, bonded to each other. The multiple repeating subunits constitute the backbone of the prepolymer.
The polyfunctional agent may have a structure of formula (1):
B(–V) z (1)
wherein B is a core of the polyfunctionalizing agent, each V is a moiety that is terminated in a reactive functional group such as a thiol group, an alkenyl group, an epoxy group, an isocyanate group, or a michael acceptor group, and z is an integer from 3 to 6, such as 3, 4, 5, or 6. In the polyfunctionalizing agent of formula (1), each-V may have, for example, -R-SH or-R-ch=ch 2 Wherein R may be, for example, C 2-10 Alkanediyl, C 2-10 Heteroalkanediyl, substituted C 2-10 Alkanediyl or substituted C 2-10 Heteroalkanediyl. When part V is reacted with another compound, part-V is produced 1 - (said to be derived from reaction with another compound). When V is-R-ch=ch 2 And reacting with, for example, thiol groups, part V 1 is-R-CH 2 –CH 2 -derived from said reaction.
The specific gravity is determined according to ISO 787-11.
Shore A hardness is measured according to ASTM D2240 using a type A durometer.
"substituted" refers to a group in which one or more hydrogen atoms are each independently replaced by the same or different substituents. Substituents may include halogen, -S (O) 2 OH、–S(O) 2 -SH, -SR, wherein R is C 1-6 Alkyl, -COOH, -NO 2 、–NR 2 Wherein each R independently comprises hydrogen and C 1-3 Alkyl, -CN, = O, C 1-10 Alkyl, -CF 3 -OH, phenyl, C 2-6 Heteroalkyl, C 5-6 Heteroaryl, C 1-10 Alkoxy or-COR, wherein R is C 1-10 An alkyl group. The substituent may be-OH, -NH 2 Or C 1-10 An alkyl group.
"tack free time" refers to the time from the first initiation of the curing reaction of the coreactive composition to the layer made from the coreactive composition no longer being tack free, where tack free is determined by applying a polyethylene sheet to the surface of the layer by hand pressure and observing whether the sealant adheres to the surface of the polyethylene sheet, where the layer is considered tack free if the polyethylene sheet is easily separated from the layer. For an actinic radiation curable co-reactive composition, tack free time refers to the time from exposure of the co-reactive composition to actinic radiation until a layer prepared from the co-reactive composition is no longer tack free.
Tensile strength and elongation were measured according to AMS 3279.
"transmission" refers to the ability to transmit a portion of the electromagnetic spectrum in the range of 360nm to 750nm, greater than 20%, greater than 30%, greater than 40% or greater than 50% of the incident radiation.
Reference is now made to certain compounds, compositions, devices, and methods of the present invention. The disclosed compounds, compositions, devices, and methods are not intended to limit the claims. On the contrary, the claims are intended to cover all alternatives, modifications and equivalents.
The present disclosure provides methods including methods of manufacturing sealing caps using three-dimensional printing. The sealing cap may be manufactured by depositing the co-reactive composition directly onto the fastener using three-dimensional printing. The deposited co-reactive composition forms a sealing cap and/or a sealing cap shell may be applied over the deposited co-reactive composition onto the faster to form a sealing cap. The sealing cap may be manufactured using three-dimensional printing. The sealing cap may also be manufactured by depositing a continuous layer of a co-reactive composition to form a sealing cap shell and filling the internal volume defined by the sealing cap shell with a further co-reactive composition, which may be the same or different from the first co-reactive composition. A sealing cap comprising a sealing cap shell and a filled interior may then be assembled over the fastener to seal the fastener.
In the context of the present disclosure, "sealing a fastener" and like terms refer to the process of placing a co-reactive composition over a fastener such that the co-reactive composition conforms to the surface of the fastener and, after curing, provides a barrier that minimizes contact of liquids, such as water, solvents, and fuels, with the fastener during the design life of the seal.
The sealing cap is typically a dome-shaped structure that fits over the extension of the fastener above the surface. Cross-sectional views of the sealing cap and fastener are shown in fig. 1A and 1B. Fig. 1A shows a view of a sealing cap 101 having an outer layer forming a shell 102 and an inner layer 103 surrounding fasteners 104 mounted to a surface 105. FIG. 1B shows a view of another example of a sealing cap having a single layer 106 surrounding a fastener 104 mounted to a surface 105.
Views of the sealing cap are shown in fig. 2A-2C. Fig. 2A shows a perspective view of the outer surface 202 of the sealing cap 201. Fig. 2B shows a cross-sectional view of the outer layer 203 of the sealing cap defining the interior volume 204. As shown in fig. 2C, the interior volume 204 may be filled with a co-reactive composition 205 to fill the volume and ready for assembly onto a fastener.
To seal the fastener, a sealing cap as shown in fig. 2C may be applied over the fastener before the internal coreactive composition 205 is fully cured. The sealing cap 203 may be at least partially cured to seal the cap to retain the co-reactive composition 205 and allow the sealing cap to be manipulated manually or automatically. The outer surface of the sealing cap may be at least partially cured or fully cured; and the inner surface of the sealing cap may be at least partially uncured or completely uncured when applied to the fastener. The sealing cap shell may also be fully cured prior to assembly of the sealing cap over the fastener. The internal coreactant composition 205 may be uncured or at least partially uncured so that a sealing cap may be applied over the fastener, and the internal coreactant composition 205 has a sufficiently low viscosity so that the internal coreactant composition 205 conforms to the contours of the fastener and other assemblies such as bolts, washers and surfaces to cover the fastener to form a viable seal. It is generally desirable that the internal coreactive composition contact the surface of the fastener and substrate without any air gaps, voids, and/or bubbles. After the sealing cap is assembled onto the fastener, the sealing cap shell and the internal co-reactive composition may be fully cured such that the co-reactive composition has not yet fully cured to seal the fastener.
The sealing cap may have a dome shape sized to cover a particular fastener. For example, the width of the base of the sealing cap (element 208 in FIG. 2B) may be, for example, 5mm to 60mm, 10mm to 40mm, or 20mm to 30mm. The dimensions of the base of the sealing cap may be, for example, greater than 5mm, greater than 10mm, greater than 20mm, greater than 30mm or greater than 40mm. The base of the sealing cap may be, for example, less than 10mm, less than 20mm, less than 30mm, less than 40mm or less than 50mm. The height of the sealing cap may be, for example, 5mm to 50mm, 10mm to 40mm or 20mm to 30mm. The height of the sealing cap may be, for example, greater than 5mm, greater than 10mm, greater than 20mm, greater than 30mm, greater than 40mm, or greater than 50mm. The height of the sealing cap may be, for example, less than 10mm, less than 20mm, less than 30mm, less than 40mm or less than 50mm.
The sealing cap may have an average thickness of, for example, 0.5mm to 25mm, 1mm to 20mm, 1.5mm to 15mm, or 2mm to 10 mm. The sealing cap may have an average thickness (207) of, for example, greater than 0.5mm, greater than 1mm, greater than 2mm, greater than 5mm, greater than 10mm, greater than 15mm, or greater than 20 mm. The sealing cap may have an average thickness of, for example, less than 1mm, less than 2mm, less than 5mm, less than 10mm, less than 15mm, or less than 20 mm.
The sealing cap may be configured to seal the fastener from exposure to solvents such as fuel and hydraulic fluid during use. For example, it may be desirable that the surface of the fastener be covered with at least 5mm of the cured solvent resistant composition.
The sealing caps provided by the present disclosure may be manufactured using three-dimensional printing. Three-dimensional printing encompasses various automated manufacturing methods in which a processor-controlled automated method is used to form a three-dimensional article. A three-dimensional printing method for manufacturing a sealing cap includes depositing one or more co-reactive compositions in successive layers to form the sealing cap.
In a first method of manufacturing a sealing cap, a continuous layer of a first co-reactive composition may be deposited directly onto a fastener and the deposited first co-reactive composition is allowed to cure in situ on the fastener to form the sealing cap.
The sealing cap may be formed by depositing a first co-reactive composition onto the fastener and then depositing a second co-reactive composition over the first co-reactive composition to form the sealing cap. The first co-reactive composition may be fully cured, partially cured, or may remain uncured prior to depositing the second co-reactive composition.
The first and second co-reactive compositions may be deposited simultaneously, for example by depositing the first and second co-reactive compositions independently using separate printing nozzles, or by co-extrusion through a single co-extrusion nozzle to deposit the first and second co-reactive compositions and optionally additional co-reactive compositions.
The first and second co-reactive compositions may have the same cure chemistry or may have different cure chemistries. Each of the first and second co-reactive compositions may independently include a compound capable of reacting with a compound in the other co-reactive composition.
The co-reactive composition may include a first compound having a first functional group and a second compound having a second functional group, wherein the functional groups react to form a cured polymer network. For co-reactive compositions having the same cure chemistry, the first functional group and the second functional group in both co-reactive compositions will be the same. For example, both the first and second coreactive compositions may be based on thiol/ene chemistry.
For co-reactive compositions that do not have the same cure chemistry but include compounds capable of co-reaction, the first functional group in the two co-reactive compositions may be the same and the second functional group may be different and capable of co-reacting with the first functional group. As one example, the first functional group may be a thiol group, and in the first co-reactive composition the second functional group may be an alkenyl group, and in the second co-reactive composition the second functional group may be an epoxy group. The second functional groups in the first and second coreactive compositions are different but still capable of reacting with the common first functional group (i.e., thiol group).
By selecting a first and a second coreactive composition that can co-react, chemical bonding between the coreactants can occur during curing. Chemical bonding at the interface between the first and second co-reactive compositions combines the two co-reactive compositions to provide a robust interface. Although chemical bonding may occur between the cured and uncured co-reactive compositions, it is desirable that the first and second co-reactive compositions, or at least a portion of the co-reactive compositions at the interface, remain uncured or at least partially uncured when they are initially combined, and then cured simultaneously to increase the extent of reaction between compounds at the interface between the two co-reactive compositions and thereby increase the chemical bonding between adjacent co-reactive compositions. Bonding between adjacent coreactive compositions may occur by physical means, such as by entanglement and/or migration of interlayer components.
A seal cap manufactured by depositing one or more co-reactive compositions directly onto a fastener using co-reactive three-dimensional printing can minimize the gap between the fastener and the co-reactive composition. The cure chemistry and viscosity of the co-reactive composition can be selected to flow and conform to the complex geometry of the fastener, and the three-dimensional printing process can be designed to continuously remove air that might otherwise be trapped between the fastener surface and the sealant. Coreactive three-dimensional printing may also facilitate the use of a variety of curing chemistries and prepolymers that are not readily accessible using the curing process used to make the sealing cap. For example, current methods of manufacturing sealing caps may involve UV curing of the sealant composition. To facilitate UV-initiated curing, the curing chemistry is typically based on free radical polymerization, and the sealant composition must be transmissive to allow UV radiation to penetrate the depth of the sealant. Thus, the cure chemistry and sealant composition of the UV-curable sealing caps may be limited. As disclosed herein, the ability to manufacture a sealing cap having multiple layers, wherein the desired properties of each layer are optimized to provide a certain function, may provide a sealing cap with superior performance properties (as compared to a sealing cap formed from a single composition). Furthermore, the use of a co-reactive composition capable of co-reacting and forming a chemical bonding layer may provide strong interfacial integrity and thereby enhance the reliability of the three-dimensional printed sealing cap under demanding aerospace use conditions. In addition, the use of three-dimensional printing to deposit the sealant composition directly onto the fastener to make the sealing cap avoids storing a stream of preformed sealing caps (which may be of various shapes and sizes). Direct in situ manufacturing of the sealing cap using three-dimensional printing under semi-automated or fully automated control facilitates an operator being able to manufacture the sealing cap on fasteners having a variety of different shapes and sizes.
The sealing cap can be made by: the first co-reactive composition is deposited directly onto the fastener using three-dimensional printing, a pre-manufactured sealing cap is applied over the deposited first co-reactive composition, and the first co-reactive composition is cured and optionally the sealing cap is cured (as needed) to seal the fastener.
As with the first method, one or more co-reactive compositions may be deposited directly onto the fastener, either sequentially or simultaneously. The preformed sealing cap may be manufactured using three-dimensional printing by depositing a continuous layer of the second coreactive composition or by other means. At least the outer surface of the sealing cap may be at least partially cured for ease of handling. The inner surface of the sealing cap may be partially cured or uncured to facilitate chemical bonding of the first co-reactive composition to the sealing cap. The preformed sealing cap may be fully cured. The preformed seal cap may include a second co-reactive composition, which may or may not be the same as the deposited co-reactive composition, have the same or different cure chemistry as the deposited co-reactive composition, be capable of co-reacting with the deposited co-reactive composition, or be non-reactive with the deposited co-reactive composition.
The method of sealing a fastener provided by the present disclosure further comprises depositing successive layers of a first co-reactive composition by three-dimensional printing to form a sealing cap shell defining an interior volume; and filling the interior volume with a second co-reactive composition to provide a sealing cap that can be secured over the fastener and cured to seal the fastener.
The first and second co-reactive compositions may be the same or different and may have the same or different cure chemistries. The first and second coreactive compositions may or may not be coreactive with each other.
The sealing cap may be partially cured or fully cured when the interior volume is filled with the second co-reactive composition. In order to facilitate chemical bonding between the sealing cap and the second co-reactive composition, it may be desirable that at least a portion of the first co-reactive composition forming the inner surface of the sealing cap is not fully cured. Further, to facilitate chemical bonding between the sealing cap and the second co-reactive composition, the first co-reactive composition may include a compound capable of reacting with a compound in the second co-reactive composition.
Filling the interior volume of the sealing cap with the second co-reactive composition may include depositing the second co-reactive composition into the interior volume using three-dimensional printing or other methods such as extrusion or filling using a spatula or other tool.
The second co-reactive composition filling the interior volume of the sealing cap may have a viscosity that facilitates the second co-reactive composition being able to conform to the surface of the fastener (which may be minimized if not eliminated as voids or air pockets). The second co-reactive composition may be uncured or partially cured upon placement of the sealing cap over the fastener.
After placement over the fastener, the sealing cap and the second coreactive composition within may be cured by any suitable method suitable for the cure chemistry of the first and second coreactive compositions.
As a modification of the present method, the sealing cap may be manufactured by depositing a continuous layer of co-reactive three-dimensional printing to form the sealing cap. In the present method, the sealing cap is manufactured in one piece and there is no separate step for manufacturing the sealing cap shell and filling the internal volume. In the present method, the outer surface of the sealing cap may be partially or fully cured to facilitate handling and placement of the sealing cap onto the fastener. The co-reactive composition in the interior volume of the sealing cap may remain uncured or partially uncured so that the uncured co-reactive composition is able to conform to and cover the fastener.
In the present method, the outer portion, the middle portion, and/or the inner portion of the sealing cap may comprise the same or different co-reactive compositions, may have the same or different cure chemistries, and/or may be co-reactive with other portions of the sealing cap. For example, the outer portion of the sealing cap may have a fast cure rate and the inner portion may have a slow cure rate. Herein, the fast and slow cure rates refer to the relative cure rates of the different portions of the sealing cap. For example, the outer portion of the sealing cap may have a shorter working time or gel time and a short tack-free time than the inner portion of the sealing cap. The outer portion provided with the sealing cap may facilitate the sealing cap to be able to maintain its shape and to be handled easily. The slower curing rate of the inner portion of the sealing cap may allow time for the material properties to fully develop. As another example, the outer surface may be rapidly cured upon exposure to actinic radiation to facilitate handling of the sealing cap.
A prefabricated sealing cap may be applied to a fastener comprising one or more layers of three-dimensional printed material. The printed material may conform to the complex surface of the fastener and provide a conformal or smooth surface to which the pre-manufactured sealing cap may be applied. By using a co-reactive composition, bonding between layers may be enhanced.
The co-reactive composition used to make the sealing cap, sealing cap shell, and/or to fill the interior volume may include a prepolymer having any suitable backbone, a prepolymer having any suitable reactive functional group, a co-reactive compound based on any suitable cure chemistry, and/or any suitable additive.
The first and second co-reactive compositions may include, for example, prepolymers having the same or different prepolymer backbones, prepolymers having the same or different reactive functional groups, co-reactive compounds having the same or different cure chemistries, co-reactive compounds having different cure rates, and/or the same or different additives. For example, the first and second coreactive compositions may include different types of ingredients and/or different amounts of ingredients. For example, the first co-reactive composition may include a first wt% of one or more ingredients and the second co-reactive composition may include a second wt% of one or more ingredients, wherein the first wt% is the same as or different from the second wt% or at least one ingredient, and the wt% is based on the total weight of the respective co-reactive composition.
As another example, the first co-reactive composition may include a first vol% of one or more ingredients and the second co-reactive composition may include a second vol% of one or more ingredients, wherein the first vol% is the same as or at least one ingredient different from the second vol% and the wt% is based on the total volume of the respective co-reactive composition.
Similarly, when cured, the first and second co-reactive compositions may have the same or different material properties, including, for example, solvent resistance, physical properties, and/or specific gravity.
The first and second co-reactive compositions may include a compound capable of reacting with a compound in the other co-reactive composition.
The co-reactive composition may include a first compound having a first functional group and a second compound including a second functional group, wherein the first functional group is reactive with the second functional group. The first and second compounds may independently comprise a monomer, a combination of monomers, a prepolymer, a combination of prepolymers, or a combination thereof.
The co-reactive composition may comprise, for example, a one-part co-reactive composition, wherein the reaction between the co-reactive compounds is initiated by exposure to energy, for example, exposure to actinic radiation.
The co-reactive composition may be formed by combining and mixing a first co-reactive component comprising a first compound having a first functional group and a second co-reactive component comprising a second compound having a second functional group, wherein the first and functional groups are reactive with the second functional group.
The co-reactive composition may include a co-reactive compound capable of reacting at a temperature of less than 50 ℃, such as less than 40 ℃, less than 30 ℃, less than 20 ℃, or less than 10 ℃ without exposure to actinic radiation or subsequent exposure to actinic radiation. For example, the coreactive compound may be reacted at a temperature of from 5 ℃ to 50 ℃, from 10 ℃ to 40 ℃, or from 15 ℃ to 25 ℃, or from 20 ℃ to 30 ℃. The coreactive composition may include coreactive compounds that coreact and cure at room temperature, where room temperature refers to a temperature of 20 ℃ to 25 ℃, 20 ℃ to 22 ℃, or about 20 ℃.
The co-reactive composition was at 25℃and 0.1 seconds -1 Up to 100 seconds -1 The viscosity at the shear rate of (3) is, for example, 200cP to 50,000,000cP, 200cP to 20,000,000cP, 1,000cP to 18,000,000cP, 5,000cP to 15,000,000cP, 5,000cP to 10,000,000cP, 5,000cP to 5,000,000cP, 5,000cP to 100,000cP, 5,000cP to 50,000cP, 5,000cP to 20,000cP, 6,000cP to 15,000cP, 7,000cP to 13,000cP, or 8,000cP to 12,000cP. The co-reactive composition was at 25℃and 0.1 seconds -1 Up to 100 seconds -1 For example, greater than 200cP, greater than 1,000cP, greater than 10,000cP, greater than 100,000cP, greater than 1,000,000cP, or greater than 10,000,000cP. The co-reactive composition was at 25℃and 0.1 seconds -1 Up to 100 seconds -1 For example, less than 100,000,000cp, less than 10,000,000cp, less than 1,000,000cp, less than 100,000cp, less than 10,000cp, or less than 1,000cp. Viscosity values using an Anton Paar MCR 302 rheometer at a temperature of 25 ℃ and 100 seconds -1 Measured with a 1mm gap at a shear rate of (2).
The coreactive composition may be formulated into a sealant composition that forms a sealant upon curing.
By sealant is meant a material that is capable of withstanding atmospheric conditions such as moisture and temperature and/or at least partially blocking the transmission of materials such as water, solvents, fuels, hydraulic fluids, and other liquids and gases. The sealant may exhibit chemical resistance, for example to fuels and Resistance to hydraulic fluid. For example, the chemical resistant material may exhibit a% swelling of less than 25%, less than 20%, less than 15% or less than 10% after immersion in a chemical at 70 ℃ for 7 days, as determined according to EN ISO 10563. The sealant may exhibit a specific viscosity to Jet Reference Fluid (JRF) type I orResistance to LD-40 hydraulic fluid.
It may be desirable for the outer portion of the sealing cap, such as the sealing cap shell, or the outer portion of the multi-layer sealing cap to include a sealant. The outer portion of the sealing cap that is exposed to the environment may act as a solvent resistant barrier. The inner portion of the sealing cap adjacent the fastener may or may not include a sealant formulation. Depending on the design, the inner portion of the sealing cap may include a cured co-reactive composition deposited directly onto the fastener, or may include a cured co-reactive composition deposited into the inner volume of the sealing cap shell, which is then assembled onto the fastener.
The outer portion of the sealing cap may include a first sealant and the inner portion may include a second sealant, wherein the first and second sealants may be the same or different.
Prepolymers used in the co-reactive compositions provided herein may have a number average molecular weight of, for example, less than 20,000da, less than 15,000da, less than 10,000da, less than 8,000da, less than 6,000da, less than 4,000da, or less than 2,000 da. The prepolymer may have a number average molecular weight of, for example, greater than 2,000Da, greater than 4,000Da, greater than 6,000Da, greater than 8,000Da, greater than 10,000Da, or greater than 15,000 Da. The prepolymer may have a number average molecular weight of, for example, 1,000Da to 20,000Da, 2,000Da to 10,000Da, 3,000Da to 9,000Da, 4,000Da to 8,000Da, or 5,000Da to 7,000 Da.
The prepolymers used in the co-reactive compositions provided herein may be liquid at 25 ℃ and may have a glass transition temperature Tg of, for example, less than-20 ℃, less than-30 ℃, or less than-40 ℃.
Prepolymers used in the co-reactive compositions provided herein may exhibit a viscosity at 25 ℃ in the range of, for example, 20 poise to 500 poise (2 pa-sec to 50 pa-sec), 20 poise to 200 poise (2 pa-sec to 20 pa-sec), or 40 poise to 120 poise (4 pa-sec to 12 pa-sec).
The co-reactive composition may include a prepolymer having any suitable polymeric backbone. For example, the polymeric backbone may be selected to impart solvent resistance to the cured co-reactive composition, impart desired physical properties such as tensile strength, elongation, young's modulus, impact resistance, or other application-related properties. The prepolymer backbone may be terminated with one or more suitable functional groups suitable for the particular cure chemistry.
For example, the prepolymer backbone may include polythioethers, polysulfides, polyformals, polyisocyanates, polyureas, polycarbonates, polyphenylene sulfides, polyethylene oxides, polystyrenes, acrylonitrile-butadiene-styrene, polycarbonates, styrene acrylonitrile, poly (methyl methacrylate), polyvinyl chloride, polybutadiene, polybutylene terephthalate, poly (p-phenylene ether), polysulfones, polyethersulfones, polyethyleneimines, polyphenylsulfones, acrylonitrile styrene acrylates, polyethylenes, syndiotactic or isotactic polypropylene, polylactic acid, polyamides, ethylene-vinyl acetate homo-or copolymers, polyurethanes, ethylene copolymers, propylene impact copolymers, polyetheretherketones, polyoxymethylene, syndiotactic Polystyrene (SPS), polyphenylene sulfide (PPS), liquid Crystal Polymers (LCP), butene homo-and copolymers, hexene homo-and copolymers; and combinations of any of the foregoing.
Examples of other suitable prepolymer backbones include polyolefins (e.g., polyethylene, linear Low Density Polyethylene (LLDPE), low Density Polyethylene (LDPE), high density polyethylene, polypropylene, and olefin copolymers), styrene/butadiene rubber (SBR), styrene/ethylene/butadiene/styrene copolymers (SEBS), butyl rubber, ethylene/propylene copolymers (EPR), ethylene/propylene/diene monomer copolymers (EPDM), polystyrene (including high impact polystyrene), poly (vinyl acetate), ethylene/vinyl acetate copolymers (EVA), poly (vinyl alcohol), ethylene/vinyl alcohol copolymers (EVOH), poly (vinyl butyral), poly (methyl methacrylate), and other acrylate polymers and copolymers (including, for exampleMethyl methacrylate polymers, methacrylate copolymers, polymers derived from one or more acrylates, methacrylates, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, and the like), olefin and styrene copolymers, acrylonitrile/butadiene/styrene (ABS), styrene/acrylonitrile polymers (SAN), styrene/maleic anhydride copolymers, isobutylene/maleic anhydride copolymers, ethylene/acrylic acid copolymers, poly (acrylonitrile), polycarbonates (PC), polyamides, polyesters, liquid Crystal Polymers (LCP), poly (lactic acid), poly (phenylene ether) (PPO), PPO-polyamide alloys, polysulfones (PSU), polyetherketones (PEK), polyetheretherketones (PEEK), polyimides, polyoxymethylene (POM) homopolymers and copolymers, polyetherimides, fluorinated ethylene propylene polymers (FEP), poly (fluoroethylene), poly (vinylidene fluoride), poly (vinylidene chloride) and poly (vinyl chloride), polyurethanes (thermoplastic and thermoset), aromatic polyamides (e.g., And->) Polytetrafluoroethylene (PTFE), polysiloxanes (including polydimethylsiloxanes, dimethylsiloxane/vinylmethylsiloxane copolymers, vinyldimethylsiloxane-terminated poly (dimethylsiloxanes)), elastomers, epoxy polymers, polyureas, alkyds, cellulosic polymers (e.g., ethylcellulose, ethylhydroxyethyl cellulose, carboxymethyl cellulose, cellulose acetate propionate, and cellulose acetate butyrate), polyethers and diols such as poly (ethylene oxide) (also known as poly (ethylene glycol)), poly (propylene oxide) (also known as poly (propylene glycol)) and ethylene oxide/propylene oxide copolymers, acrylic latex polymers, polyester acrylate oligomers and polymers, polyester glycol diacrylate polymers, and UV curable resins.
The coreactive composition may include a prepolymer including an elastomeric backbone.
"elastomer," "elastic," and the like refer to materials that have "rubbery" properties and generally have a low Young's modulus and high tensile strain. The elastomer may have a tensile strain (elongation at break) of about 100% to about 2,000%. The elastomer may exhibit a tear strength of, for example, 50kN/m to 200kN/m, as determined according to ASTM D624. The young's modulus of the elastomer may be in the range of, for example, 0.5MPa to 30MPa, for example, 1MPa to 6MPa, as determined according to ASTM D412.4893.
Examples of suitable prepolymers having an elastomeric backbone include polyethers, polybutadiene, fluoroelastomers, perfluoroelastomers, ethylene/acrylic acid copolymers, ethylene propylene diene terpolymers, nitriles, polythioamines, polysiloxanes, chlorosulfonated polyethylene rubbers, isoprene, chloroprene, polysulfides, polythioethers, silicones, styrene butadiene, and combinations of any of the foregoing. The elastic prepolymer may include a polysiloxane, such as polymethylhydrosiloxane, polydimethylsiloxane, polyethylhydrosiloxane, polydiethylsiloxane, or a combination of any of the foregoing. The elastic prepolymer may include functional groups having low reactivity with amine and isocyanate groups, such as silanol groups.
The co-reactive composition may comprise a sulfur-containing prepolymer or a combination of sulfur-containing prepolymers. The sulfur-containing prepolymer may impart fuel resistance to the cured sealant.
"Sulfur-containing prepolymer" means a prepolymer having one or more sulfide-S in the backbone of the prepolymer n -prepolymers of groups, wherein n may be, for example, 1 to 6. Prepolymers containing only thiol or other sulfur-containing groups as terminal or pendant groups of the prepolymer are not encompassed in sulfur-containing prepolymers. The prepolymer backbone refers to the portion of the prepolymer having repeating segments. Thus, it has the structure HS-R-R (-CH) 2 –SH)–[–R–(CH 2 ) 2 –S(O) 2 –(CH 2 )–S(O) 2 ] n –CH＝CH 2 Wherein each R is a moiety containing no sulfur atoms is not included in the sulfur-containing prepolymer. Having the structure HS-R-R (-CH) 2 –SH)–[–R–(CH 2 ) 2 –S(O) 2 –(CH 2 )–S(O) 2 ]–CH＝CH 2 Wherein at least one R is a prepolymer containing sulfur atoms without any sulfur-containing moiety such as a thioether groupDivided portions) are included in the sulfur-containing prepolymer.
Sulfur-containing prepolymers with high sulfur content can impart chemical resistance to the cured co-reactive composition. For example, the sulfur-containing prepolymer backbone can have a sulfur content of greater than 10wt%, greater than 12wt%, greater than 15wt%, greater than 18wt%, greater than 20wt%, or greater than 25wt%, where wt% is based on the total weight of the prepolymer backbone. The chemical resistant prepolymer backbone can have a sulfur content of, for example, 10wt% to 25wt%, 12wt% to 23wt%, 13wt% to 20wt%, or 14wt% to 18wt%, where wt% is based on the total weight of the prepolymer backbone.
The co-reactive composition may comprise, for example, 40wt% to 80wt%, 40wt% to 75wt%, 45wt% to 70wt%, or 50wt% to 70wt% of the sulfur-containing prepolymer or combination of sulfur-containing prepolymers, wherein wt% is based on the total weight of the co-reactive composition. The co-reactive composition may include, for example, greater than 40wt%, greater than 50wt%, greater than 60wt%, greater than 70wt%, greater than 80wt%, or greater than 90wt% of the sulfur-containing prepolymer or combination of sulfur-containing prepolymers, wherein the wt% is based on the total weight of the co-reactive composition. The co-reactive composition may include, for example, less than 90wt%, less than 80wt%, less than 70wt%, less than 60wt%, less than 50wt%, or less than 40wt% of the sulfur-containing prepolymer or a combination of sulfur-containing prepolymers, wherein the wt% is based on the total weight of the co-reactive composition.
Examples of prepolymers having a sulfur-containing backbone include polythioether prepolymers, polysulfide prepolymers, sulfur-containing polyformal prepolymers, monosulfide prepolymers, and combinations of any of the foregoing.
The co-reactive composition may comprise a polythioether prepolymer or a combination of polythioether prepolymers.
The polythioether prepolymer may comprise a polythioether prepolymer comprising at least one portion having the structure of formula (2), a thiol-terminated polythioether prepolymer of formula (2 a), a terminally modified polythioether of formula (2 b), or a combination of any of the foregoing:
-S-R 1 -[S-A-S-R 1 -] n -S-(2)
HS-R 1 -[S-A-S-R 1 -] n -SH(2a)
R 3 -S-R 1 -[S-A-S-R 1 -] n -S-R 3 (2b)
wherein the method comprises the steps of
n may be an integer from 1 to 60;
each R 3 May independently be a moiety comprising a terminal reactive group;
each R 1 Can be independently selected from C 2-10 Alkanediyl, C 6-8 Cycloalkanediyl, C 6-14 Alkanecycloalkanediyl, C 5-8 Heterocycloalkanediyl and- [ (CHR) p -X-] q (CHR) r -, wherein
p may be an integer from 2 to 6;
q may be an integer from 1 to 5;
r may be an integer from 2 to 10;
each R may be independently selected from hydrogen and methyl; and is also provided with
Each X may be independently selected from O, S and S-S; and is also provided with
Each a may independently be a moiety derived from a polyvinyl ether of formula (3) and a polyalkenyl functionalizing agent of formula (4):
CH 2 ＝CH-O-(R 2 -O) m -CH＝CH 2 (3)
B(-R 4 -CH＝CH 2 ) z (4)
wherein the method comprises the steps of
m may be an integer of 0 to 50;
each R 2 Can be independently selected from C 1-10 Alkanediyl, C 6-8 Cycloalkanediyl, C 6-14 Alkane cycloalkanediyl and- [ (CHR) p -X-] q (CHR) r -, wherein p, q, R, R and X are as for R 1 The definitions are the same;
b represents a z-valent polyene based multi-functionalizing agent B (-R) 7 -CH＝CH 2 ) z Wherein
z may be an integer from 3 to 6; and is also provided with
Each R 4 Can be independently selected from C 1-10 Alkanediyl, C 1-10 HeteroalkanesHydrocarbadiyl, substituted C 1-10 Alkanediyl and substituted C 1-10 Heteroalkanediyl.
In the moiety of formula (2) and the prepolymers of formulae (2 a) and (2 b), R 1 May be C 2-10 Alkanediyl.
In the moiety of formula (2) and the prepolymers of formulae (2 a) and (2 b), R 1 May be- [ (CHR) p -X-] q (CHR) r -。
In the moiety of formula (2) and the prepolymers of formulae (2 a) and (2 b), X may be selected from O and S, and thus- [ (CHR) p -X-] q (CHR) r Can be- [ (CHR) p -O-] q (CHR) r -or- [ (CHR) p -S-] q (CHR) r -. P and r may be equal, for example, where P and r may both be 2.
In the moiety of formula (2) and the prepolymers of formulae (2 a) and (2 b), R 1 Can be selected from C 2-6 Alkanediyl and- [ (CHR) p -X-] q (CHR) r -。
In the moiety of formula (2) and the prepolymers of formulae (2 a) and (2 b), R 1 May be- [ (CHR) p -X-] q (CHR) r -, and X may be O, or X may be S.
In the moiety of formula (2) and the prepolymers of formulae (2 a) and (2 b), wherein R 1 May be- [ (CHR) p -X-] q (CHR) r -, p may be 2, r may be 2, q may be 1, and X may be S; or p may be 2, q may be 2, r may be 2, and X may be O; or p may be 2, r may be 2, q may be 1, and X may be O.
In the moiety of formula (2) and the prepolymers of formulae (2 a) and (2 b), R 1 May be- [ (CHR) p -X-] q (CHR) r -each R may be hydrogen, or at least one R may be methyl.
In the moiety of formula (2) and the prepolymers of formulae (2 a) and (2 b), R 1 Can be- [ (CH) 2 ) p -X-] q (CH 2 ) r -, wherein each X may be independently selected from O and S.
In the moiety of formula (2) and formulas (2 a) and (2 b)(2b) R in the prepolymer of (C) 1 Can be- [ (CH) 2 ) p -X-] q (CH 2 ) r -, each X may be O or each X may be S.
In the moiety of formula 2) and the prepolymers of formulae (2 a) and (2 b), R 1 Can be- [ (CH) 2 ) p -X-] q (CH 2 ) r Where p may be 2, X may be O, q may be 2, r 2 May be ethanediyl, m may be 2, and n may be 9.
In the moiety of formula (2) and the prepolymers of formulae (2 a) and (2 b), each R 1 Can be derived from 1, 8-dimercapto-3, 6-dioxaoctane (DMDO; 2,2- (ethane-1, 2-diylbis (sulfanyl)) bis (ethane-1-thiol)), or each R 1 May be derived from dimercaptodiethylsulfide (DMDS; 2,2' -thiobis (ethyl-1-thiol)) and combinations thereof.
In the moiety of formula (2) and the prepolymers of formulae (2 a) and (2 b), each p may be independently selected from 2, 3, 4, 5 and 6. Each p may be the same and may be 2, 3, 4, 5 or 6.
In the moiety of formula (2) and the prepolymers of formulae (2 a) and (2 b), each q may independently be 1,2, 3, 4 or 5. Each q may be the same and may be 1,2, 3, 4 or 5.
In the moiety of formula (2) and the prepolymers of formulae (2 a) and (2 b), each r may independently be 2, 3, 4, 5, 6, 7, 8, 9 or 10. Each r may be the same and may be 2, 3, 4, 5, 6, 7, 8, 9 or 10.
In the moiety of formula (2) and the prepolymers of formulae (2 a) and (2 b), each r may independently be an integer from 2 to 4, from 2 to 6 or from 2 to 8.
In the divinyl ether of formula (3), m may be an integer of 0 to 50, for example 0 to 40, 0 to 20, 0 to 10, 1 to 50, 1 to 40, 1 to 20, 1 to 10, 2 to 50, 2 to 40, 2 to 20 or 2 to 10.
In the divinyl ether of formula (3), each R 2 Can be independently selected from C 2-10 N-alkanediyl radical, C 3-6 Branched alkanediyl groups and- [ (CH) 2 ) p -X-] q (CH 2 ) r -group。
In the divinyl ether of formula (3), each R 2 Can be independently C 2-10 N-alkanediyl groups, such as methanediyl, ethanediyl, n-propanediyl or n-butanediyl.
In the divinyl ether of formula (3), each R 2 Can independently include- [ (CH) 2 ) p -X-] q (CH 2 ) r -a group, wherein each X may be O or S.
In the divinyl ether of formula (3), each R 2 Can independently include- [ (CH) 2 ) p -X-] q (CH 2 ) r -a group.
In the divinyl ether of formula (3), each m may independently be an integer from 1 to 3. Each m may be the same and may be 1, 2 or 3.
In the divinyl ether of formula (3), each R 2 Can be independently selected from C 2-10 N-alkanediyl radical, C 3-6 Branched alkanediyl groups and- [ (CH) 2 ) p -X-] q (CH 2 ) r -a group.
In the divinyl ether of formula (3), each R 2 Can be independently C 2-10 N-alkanediyl groups.
In the divinyl ether of formula (3), each R 2 Can be independently- [ (CH) 2 ) p -X-] q (CH 2 ) r -a group, wherein each X may be O or S.
In the divinyl ether of formula (3), each R 2 Can be independently- [ (CH) 2 ) p -X-] q (CH 2 ) r -a group wherein each X may be O or S and each p may independently be 2, 3, 4, 5 and 6.
In the divinyl ether of formula (3), each p may be the same and may be 2, 3, 4, 5 or 6.
In the divinyl ether of formula (3), each R 2 Can be independently- [ (CH) 2 ) p -X-] q (CH 2 ) r -a group wherein each X may be OOr S, and each q may independently be 1, 2, 3, 4, or 5.
In the divinyl ether of formula (3), each q may be the same, and may be 1, 2, 3, 4 or 5.
In the divinyl ether of formula (3), each R 2 Can be independently- [ (CH) 2 ) p -X-] q (CH 2 ) r -a group wherein each X may be O or S and each r may independently be 2, 3, 4, 5, 6, 7, 8, 9 or 10.
In the divinyl ether of formula (3), each r may be the same and may be 2, 3, 4, 5, 6, 7, 8, 9 or 10. In the divinyl ether of formula (3), each r may independently be an integer from 2 to 4, from 2 to 6, or from 2 to 8.
Examples of suitable divinyl ethers include ethylene glycol divinyl ether (EG-DVE), butylene glycol divinyl ether (BD-DVE), hexylene glycol divinyl ether (HD-DVE), diethylene glycol divinyl ether (DEG-DVE), triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, polytetrahydrofuranyl divinyl ether, cyclohexanedimethanol divinyl ether, and combinations of any of the foregoing.
The divinyl ether may include a sulfur-containing divinyl ether. Examples of suitable sulfur-containing divinyl ethers are disclosed, for example, in PCT publication No. WO 2018/085650.
In the moiety of formula (3), each a may be independently derived from a polyalkenyl functionalizing agent. The polyalkenyl-based functionalizing agent may have the structure of formula (4) wherein z may be 3, 4, 5 or 6.
In the polyolefin-based functionalizing agent of the formula (4), each R 4 Can be independently selected from C 1-10 Alkanediyl, C 1-10 Heteroalkanediyl, substituted C 1-10 Alkanediyl or substituted C 1-10 Heteroalkanediyl. The one or more substituent groups may be selected from, for example, -OH, = O, C 1-4 Alkyl and C 1-4 An alkoxy group. The one or more heteroatoms may be selected from, for example, O, S and combinations thereof.
Examples of suitable polyallylamine functionalizing agents include triallyl cyanurate (TAC), triallyl isocyanurate (TAIC), 1,3, 5-triallyl-1, 3, 5-triazin-2, 4, 6-trione), 1, 3-bis (2-methylallyl) -6-methylene-5- (2-oxopropyl) -1,3, 5-triazin-one-2, 4-dione, tris (allyloxy) methane, pentaerythritol triallyl ether, 1- (allyloxy) -2, 2-bis ((allyloxy) methyl) butane, 2-prop-2-ethoxy-1, 3, 5-tri (prop-2-enyl) benzene, 1,3, 5-tri (prop-2-enyl) -1,3, 5-triazin-2, 4-dione and 1,3, 5-tri (2-methylallyl) -1,3, 5-triazin-2, 4-dione, and any combination of the foregoing trivinyl ethers.
In the moiety of formula (2) and the prepolymers of formulae (2 a) - (2 b), the molar ratio of the moiety derived from the divinyl ether to the moiety derived from the polyalkenyl functionalizing agent may be, for example, 0.9mol% to 0.999mol%, 0.95mol% to 0.99mol%, or 0.96mol% to 0.99mol%.
In the moiety of formula (2) and the prepolymers of formulae (2 a) - (2 b), each R 1 May be- (CH) 2 ) 2 -O-(CH 2 ) 2 -O-(CH 2 ) 2 -; each R 2 May be- (CH) 2 ) 2 -; and m may be an integer of 1 to 4.
In the moiety of formula (2) and the prepolymers of formulae (2 a) - (2 b), R 2 Can be derived from divinyl ethers such as diethylene glycol divinyl ether, polyalkenyl functionalizing agents such as triallyl cyanurate, or combinations thereof.
In the moiety of formula (2) and the prepolymers of formulae (2 a) - (2 b), each a may be independently selected from the moiety of formula (3 a) and the moiety of formula (4 a):
-(CH 2 ) 2 -O-(R 2 -O) m -(CH 2 ) 2 -(3a)
B{-R 4 -(CH 2 ) 2 -} 2 {-R 4 -(CH 2 ) 2 -S-[-R 1 -S-A-S-R 1 ] n -SH} z-2 (4a)
wherein m, R 1 、R 2 、R 4 The definitions of A, B, m, n and z are as in formula (2), formula (3) and formula (4).
In the moiety of formula (3) and the prepolymers of formulae (2 a) - (2 b),
each R 1 May be- (CH) 2 ) 2 -O-(CH 2 ) 2 -O-(CH 2 ) 2 -; each R 2 May be- (CH) 2 ) 2 -; m may be an integer from 1 to 4; and a polyfunctionalizing agent B (-R) 4 -CH＝CH 2 ) z Comprises triallyl cyanurate wherein z is 3 and each R 4 is-O-CH 2 -CH＝CH 2 。
Methods for synthesizing sulfur-containing polythioethers are disclosed, for example, in U.S. Pat. No. 6,172,179.
The backbone of the thiol-terminated polythioether prepolymer can be modified to improve properties of sealants and coatings prepared using the polythioether prepolymer, such as adhesion, tensile strength, elongation, UV resistance, hardness, and/or flexibility. For example, adhesion promoting groups, antioxidants, metal ligands, and/or urethane linkages can be incorporated into the backbone of the polythioether prepolymer to improve one or more performance attributes. Examples of backbone modified polythioether prepolymers are disclosed in, for example, U.S. patent No. 8,138,273 (containing urethane), U.S. patent No. 9,540,540 (containing sulfone), U.S. patent No. 8,952,124 (containing bis (sulfonyl) alkanol), U.S. patent No. 9,382,642 (containing metal ligand), U.S. application publication No. 2017/014208 (containing antioxidant), PCT international publication No. WO 2018/085650 (containing sulfur divinyl ether), and PCT international publication No. WO 2018/031532 (containing urethane). Polythioether prepolymers include the prepolymers described in U.S. application publication Nos. 2017/0369737 and 2016/0090507.
Examples of suitable thiol-terminated polythioether prepolymers are disclosed, for example, in U.S. Pat. No. 6,172,179. The thiol-terminated polythioether prepolymer may comprise P3.1E、/>P3.1 E-2.8、/>L56086 or a combination of any of the foregoing, each of which is commercially available from PPG Aerospace. These->The product is comprised in thiol-terminated polythioether prepolymers of formulae (2), (2 a), and (2 b). Thiol-terminated polythioethers include the prepolymer described in U.S. Pat. No. 7,390,859 and urethane-containing polythiols described in U.S. application publication Nos. 2017/0369757 and 2016/0090507.
The sulfur-containing prepolymer may include polysulfide prepolymers or a combination of polysulfide prepolymers.
Polysulfide prepolymers are those containing one or more polysulfide linkages in the prepolymer backbone (i.e., -S x -bonds), wherein x is 2 to 4. Polysulfide prepolymers may have two or more sulfur-sulfur bonds. Suitable thiol-terminated polysulfide prepolymers may be sold under the trade name respectivelyAnd Thiokol- & lt- & gt>Commercially available from, for example, akzo nobel and Toray Industries, inc.
Examples of suitable polysulfide prepolymers are disclosed in, for example, U.S. patent No. 4,623,711; 6,172,179; 6,509,418; 7,009,032; and 7,879,955.
Examples of suitable thiol-terminated polysulfide prepolymers includeG polysulfides, e.g.G1、/>G4、/>G10、/>G12、/>G21、/>G22、/>G44、/>G122 and->G131, which is commercially available from Akzo Nobel. For example- >Suitable thiol-terminated polysulfide prepolymers, such as G resins, are liquid thiol-terminated polysulfide prepolymers that are a blend of difunctional and trifunctional molecules, wherein the difunctional thiol-terminated polysulfide prepolymers have the structure of formula (5), and the trifunctional thiol-terminated polysulfide polymers may have the structure of formula (6):
HS-(R 5 -S-S-) d -R 5 -SH (5)
HS-(R 5 -S-S-) a -CH 2 -CH{-CH 2 -(S-S-R 5 -) b -SH}{-(S-S-R 5 -) c -SH} (6)
wherein each R is 5 Is- (CH) 2 ) 2 -O-CH 2 -O-(CH 2 ) 2 -, and d=a+b+c, where d may have a value of 7 to 38, depending on the trifunctional crosslinking agent (1, 2, 3-trichloropropane) used during the synthesis of the polysulfide prepolymerAn alkane; TCP).The G polysulfide can have a number average molecular weight of less than 1,000da to 6,500da, an SH content of 1% to greater than 5.5%, and a crosslink density of 0% to 2.0%.
The polysulfide prepolymer may further comprise a terminally modified polysulfide prepolymer having the structure of formula (5 a), a terminally modified polysulfide prepolymer having the structure of formula (6 a), or a combination thereof:
R 3 -S-(R 5 -S-S-) d -R 5 -S-R 3 (5a)
R 3 -S-(R 5 -S-S-) a -CH 2 -CH{-CH 2 -(S-S-R 5 -) b -S-}{-(S-S-R 5 -) c -S-R 3 } (6a)
wherein d, a, b, c and R 5 As defined in formula (6) and formula (7), and R 3 Is a moiety comprising a terminal reactive group.
Examples of suitable thiol-terminated polysulfide prepolymers also include those available from Toray Industries, incLP polysulfides, e.g.) >LP2、/>LP3、Thiokol TM LP12、/>LP23、/>LP33 and->LP55。/>The LP polysulfides have a number average molecular weight of 1,000Da to 7,500Da, a-SH content of 0.8% to 7.7%, and a crosslink density of 0% to 2%. Thiokol TM The LP polysulfide prepolymer has the structure of formula (7), and the end-modified polysulfide prepolymer may have the structure of formula (7 a):
HS-[(CH 2 ) 2 -O-CH 2 -O-(CH 2 ) 2 -S-S-] e -(CH 2 ) 2 -O-CH 2 -O-(CH 2 ) 2 -SH(7)
R 3 -S-[(CH 2 ) 2 -O-CH 2 -O-(CH 2 ) 2 -S-S-] e -(CH 2 ) 2 -O-CH 2 -O-(CH 2 ) 2 -S-R 3 (7a)
wherein e may be such that the number average molecular weight is an integer from 1,000Da to 7,500Da, such as for example 8 to 80, and each R 6 Is a moiety comprising a terminal reactive functional group.
The thiol-terminated sulfur-containing prepolymer may include Thiokl-Polysulfide, & gt>G polysulfide or a combination thereof.
The polysulfide prepolymer may include polysulfide prepolymers comprising a moiety of formula (7), thiol-terminated polysulfide prepolymers of formula (7 a), end-modified polysulfide prepolymers of formula (7 b), or a combination of any of the foregoing:
-R 6 -(S y -R 6 ) t -(7)
HS-R 6 -(S y -R 6 ) t -SH(7a)
R 3 -S-R 6 -(S y -R 6 ) t -S-R 3 (7b)
wherein the method comprises the steps of
t may be an integer from 1 to 60;
y may have an average value in the range of 1.0 to 1.5;
each R may be independently selected from branched alkanediyl, branched arenediyl, and having the structure- (CH) 2 ) p –O–(CH 2 ) q –O–(CH 2 ) r -a portion in which
q may be an integer from 1 to 8;
p may be an integer from 1 to 10; and is also provided with
r may be an integer from 1 to 10; and is also provided with
Each R 3 Is a moiety comprising a terminal reactive functional group.
In the moiety of formula (7) and the prepolymers of formulae (7 a) - (7 b), 0% to 20% of R 6 The groups may include branched alkane diyl or branched arene diyl, and from 80% to 100% R 6 The radical may be- (CH) 2 ) p –O–(CH 2 ) q –O–(CH 2 ) r –。
In the moiety of formula (7) and the prepolymers of formulae (7 a) - (7 b), the branched alkanediyl or branched arenediyl may be-R (-A) f -wherein R is a hydrocarbon group, f is 1 or 2, and a is a branching point. The branched alkanediyl may have the structure-CH 2 (–CH(–CH 2 –)–)–。
Examples of thiol-terminated polysulfide prepolymers of formulas (7 a) and (7 b) are disclosed in, for example, U.S. application publication number 2016/0152775, U.S. patent No. 9,079,833, and U.S. patent No. 9,663,619.
The sulfur-containing prepolymer may comprise a sulfur-containing polyformal prepolymer or a combination of sulfur-containing polyformal prepolymers. Sulfur-containing polyformal prepolymers useful in sealant applications are disclosed, for example, in U.S. patent No. 8,729,216 and U.S. patent No. 8,541,513.
The polysulfide prepolymer may include polysulfide prepolymers comprising a moiety of formula (8), thiol-terminated polysulfide prepolymers of formula (8 a), end-modified polysulfide prepolymers of formula (8 b), or a combination of any of the foregoing:
-(R 7 -O-CH 2 -O-R 7 -S s -) g-1 -R 7 -O-CH 2 -O-R 7 -(8)
HS-(R 7 -O-CH 2 -O-R-S s -) g-1 -R 7 -O-CH 2 -O-R 7 -SH(8a)
R 3 -S-(R 7 -O-CH 2 -O-R 7 -S s -) g-1 -R 7 -O-CH 2 -O-R 7 -S-R 3 (8b)
wherein R is 7 Is C 2-4 Alkanediyl, s is an integer from 1 to 8, and g is an integer from 2 to 370; and each R 3 Independently a moiety comprising a terminal reactive functional group.
The moiety of formula (8) and the prepolymers of formulae (8 a) - (8 b) are disclosed in, for example, JP 62-53354.
The sulfur-containing polyformal prepolymer may include a moiety of formula (9), a thiol-terminated sulfur-containing polyformal prepolymer of formula (9 a), a terminal-modified sulfur-containing polyformal prepolymer of formula (9 b), a thiol-terminated sulfur-containing polyformal prepolymer of formula (9 c), a terminal-modified sulfur-containing polyformal prepolymer of formula (9 d), or a combination of any of the foregoing:
-R 8 -(S) p -R 8 -[O-C(R 9 ) 2 -O-R 8 -(S) v -R 8 -] h -(9)
R 10 -R 8 -(S) p -R 8 -[O-C(R 9 ) 2 -O-R 8 -(S) v -R 8 -] h -R 10 (9a)
R 3 -R 8 -(S) p -R 8 -[O-C(R 9 ) 2 -O-R 8 -(S) v -R 8 -] h -R 3 (9b)
{R 10 -R 8 -(S) p -R 8 -[O-C(R 9 ) 2 -O-R 8 -(S) v -R 8 -] h -O-C(R 9 ) 2 -O-} m Z(9c)
{R 3 -R 8 -(S) p -R 8 -[O-C(R 9 ) 2 -O-R 8 -(S) v -R 8 -] h -O-C(R 9 ) 2 -O-} m Z(9d)
wherein h may be an integer from 1 to 50; each v may be independently selected from 1 and 2; each R 8 May be C 2-6 An alkanediyl group; and each R 9 Can be independently selected from hydrogen, C 1-6 Alkyl, C 7-12 Phenylalkyl, substituted C 7-12 Phenylalkyl, C 6-12 Cycloalkylalkyl, substituted C 6-12 Cycloalkylalkyl, C 3-12 Cycloalkyl, substituted C 3-12 Cycloalkyl, C 6-12 Aryl and substituted C 6-12 An aryl group; each R 10 Is a moiety comprising a terminal thiol group; and each R 3 Independently a moiety comprising a terminal reactive functional group other than a thiol group; and Z may be derived from an m-valent parent polyol Z (OH) m Is a core of (a).
The sulfur-containing prepolymer may comprise a monosulfide prepolymer or a combination of monosulfide prepolymers.
The monosulfide prepolymer can include a moiety of formula (10), a thiol-terminated monosulfide prepolymer of formula (10 a), a thiol-terminated monosulfide prepolymer of formula (10 b), an end-modified monosulfide prepolymer of formula (10 c), an end-modified monosulfide prepolymer of formula (10 d), or a combination of any of the foregoing:
-S-R 13 -[S-(R 11 -X) w -(R 12 -X) u -R 13 -] x -S-(10)
HS-R 13 -[S-(R 11 -X) w -(R 12 -X) u -R 13 -] x -SH(10a)
{HS-R 13 -[S-(R 11 -X) w -(R 12 -X) u -R 13 -] x -S-V'-} z B(10b)
R 3 -S-R 13 -[S-(R 11 -X) w -(R 12 -X) u -R 13 -] x -S-R 3 (10c)
{R 3 -S-R 13 -[S-(R 11 -X) w -(R 12 -X) u -R 13 -] x -S-V'-} z B(10d)
wherein the method comprises the steps of
Each R 11 Can be independently selected from C 2-10 Alkanediyl radicals, e.g. C 2-6 An alkanediyl group; c (C) 2-10 Branched alkanediyl radicals, e.g. C 3-6 Branched alkanediyl or C having one or more side groups 3-6 A branched alkanediyl group, which may be for example an alkyl group, such as a methyl or ethyl group; c (C) 6-8 Cycloalkanediyl; c (C) 6-14 Alkylcycloalkanediyl radicals, e.g. C 6-10 An alkyl cycloalkanediyl group; and C 8-10 Alkyl arene diradicals;
each R 12 Can be independently selected from hydrogen, C 1-10 N-alkanediyl, e.g. C 1-6 N-alkanediyl, C 2-10 Branched alkanediyl radicals, e.g. C having one or more side groups 3-6 A branched alkanediyl group, which may be for example an alkyl group, such as a methyl or ethyl group; c (C) 6-8 Cycloalkanediyl; c (C) 6-14 Alkylcycloalkanediyl radicals, e.g. C 6-10 An alkyl cycloalkanediyl group; and C 8-10 Alkyl arene diradicals;
each R 13 Can be independently selected from hydrogen, C 1-10 N-alkanediyl, e.g. C 1-6 N-alkanediyl, C 2-10 Branched alkanediyl radicals, e.g. C having one or more side groups 3-6 A branched alkanediyl group, which may be for example an alkyl group, such as a methyl or ethyl group; c (C) 6-8 A cycloalkanediyl group; c (C) 6-14 Alkylcycloalkanediyl radicals, e.g. C 6-10 An alkyl cycloalkanediyl group; and C 8-10 Alkyl arene diradicals;
each X may be independently selected from O and S;
w may be an integer from 1 to 5;
u may be an integer from 0 to 5; and is also provided with
x may be an integer from 1 to 60, for example from 2 to 60, 3 to 60 or 25 to 35;
each R 3 Independently selected from reactive functional groups;
b represents a z-valent polyfunctionalizing agent B (-V) z Wherein:
z may be an integer from 3 to 6; and is also provided with
Each V may be a moiety comprising a terminal group that reacts with a thiol group;
each-V' -may be derived from the reaction of-V with a thiol.
Methods of synthesizing thiol-terminated monosulfides comprising a moiety of formula (10) or prepolymers of formulas (10 b) - (10 c) are disclosed, for example, in U.S. patent No. 7,875,666.
The monosulfide prepolymer can include a moiety of formula (11), a thiol-terminated monosulfide prepolymer including a moiety of formula (11 a), a thiol-terminated monosulfide prepolymer including formula (11 b), a thiol-terminated monosulfide prepolymer of formula (11 c), a thiol-terminated monosulfide prepolymer of formula (11 d), or a combination of any of the foregoing:
-[S-(R 14 -X) w -C(R 15 ) 2 -(X-R 14 ) q -] x -S-(11)
H-[S-(R 14 -X) w -C(R 15 ) 2 -(X-R 14 ) u -] x -SH(11a)
R 3 -[-S-(R 14 -X) w -C(R 15 ) 2 -(X-R 14 ) u -] x -S-R 3 (11b)
{H-[S-(R 14 -X) w -C(R 15 ) 2 -(X-R 14 ) u -] x -S-V'-} z B(11c)
{R 3 -[S-(R 14 -X) w -C(R 15 ) 2 -(X-R 14 ) u -] x -S-V'-} z B(11d)
Wherein the method comprises the steps of
Each R 14 Can be independently selected from C 2-10 Alkanediyl radicals, e.g. C 2-6 An alkanediyl group; c (C) 3-10 Branched alkanediyl radicals, e.g. C 3-6 Branched alkane diyl orC having one or more side groups 3-6 A branched alkanediyl group, which may be for example an alkyl group, such as a methyl or ethyl group; c (C) 6-8 Cycloalkanediyl; c (C) 6-14 Alkylcycloalkanediyl radicals, e.g. C 6-10 An alkyl cycloalkanediyl group; and C 8-10 Alkyl arene diradicals;
each R 15 Can be independently selected from hydrogen, C 1-10 N-alkanediyl, e.g. C 1-6 N-alkanediyl, C 3-10 Branched alkanediyl radicals, e.g. C having one or more side groups 3-6 A branched alkanediyl group, which may be for example an alkyl group, such as a methyl or ethyl group; c (C) 6-8 A cycloalkanediyl group; c (C) 6-14 Alkylcycloalkanediyl radicals, e.g. C 6-10 An alkyl cycloalkanediyl group; and C 8-10 Alkyl arene diradicals;
each X may be independently selected from O and S;
w may be an integer from 1 to 5;
u may be an integer from 1 to 5;
x may be an integer from 1 to 60, for example from 2 to 60, 3 to 60 or 25 to 35;
each R 3 Is a moiety comprising a terminal functional group;
b represents a z-valent polyfunctionalizing agent B (-V) z Wherein:
z may be an integer from 3 to 6; and is also provided with
Each V may be a moiety comprising a terminal group that reacts with a thiol group;
each-V' -may be derived from the reaction of-V with a thiol.
Methods for synthesizing monosulfides of formulas (11) - (11 d) are disclosed, for example, in U.S. patent No. 8,466,220.
The co-reactive composition may include a co-reactive compound having any suitable co-reactive functional group.
The first co-reactive compound may include one or more first functional groups and the second co-reactive compound may include one or more second functional groups, wherein the one or more first functional groups may react with the one or more second functional groups.
The functional group or combination of functional groups may be selected to achieve, for example, a desired cure rate. For example, for ease of handling, it may be desirable for the outer portion of the sealing cap to have a fast cure rate for ease of handling. Other portions of the seal may have a slow cure rate to allow for the formation of surface bonds, bonds between coreactive compositions, and/or desired physical properties.
For example, the first functional group may comprise a thiol group, and the second functional group may comprise a thiol group, an alkenyl group, an alkynyl group, an epoxy group, a michael acceptor group, an isocyanate group, or a combination of any of the foregoing.
The first functional group may comprise, for example, an isocyanate, and the second functional group may comprise a hydroxyl group, an amine group, a thiol group, or a combination of any of the foregoing.
The first functional group may include, for example, an epoxy group, and the second functional group may include an epoxy group.
The first functional group may comprise, for example, a michael acceptor group, and the second functional group may comprise a michael donor group.
The first functional group may include, for example, a carboxylic acid group, and the second functional group may include an epoxy group.
The first functional group may include, for example, a cyclic carbonate group, an acetoacetate group, or an epoxy group; and the second functional group may comprise a primary amine group or a secondary amine group.
The first functional group may comprise a michael acceptor group, such as a (meth) acrylate group, cyanoacrylate, vinyl ether, vinyl pyridine, or an α, β -unsaturated carbonyl group, and the second functional group may comprise a malonate group, acetylacetonate, nitroalkane, or other reactive alkenyl group.
The first functional group may comprise an amine and the second functional group may comprise a member selected from the group consisting of epoxy groups, isocyanate groups, acrylonitrile, carboxylic acids (including esters and anhydrides), aldehydes, or ketones.
Suitable co-reactive functional groups are described, for example, in noon, the thirteenth conference on organic coating science and technology international (Proceedings of the XIIIth International Conference in Organic Coatings Science and Technology), attle, 1987, page 251; and Tillet et al, polymer science Advances (Progress in Polymer Science), 36 (2011), 191-217.
The functional groups may be selected to co-react at a temperature of, for example, less than 50 ℃, less than 40 ℃, less than 30 ℃, less than 20 ℃, or less than 10 ℃. The functional groups may be selected to co-react at a temperature of, for example, greater than 5 ℃, greater than 10 ℃, greater than 20 ℃, greater than 30 ℃, or greater than 40 ℃. The functional groups may be selected to co-react at a temperature of, for example, 5 ℃ to 50 ℃, 10 ℃ to 40 ℃, 15 ℃ to 35 ℃, or 20 ℃ to 30 ℃.
The cure rate of any of these co-reactive chemistries may be altered by including a suitable catalyst or combination of catalysts in the co-reactive composition. The cure rate of any of these co-reactive chemistries can be altered by increasing or decreasing the temperature of the co-reactive composition. For example, while the co-reactive composition may cure at a temperature of less than 30 ℃, heating the co-reactive composition may accelerate the reaction rate, which may be desirable in some circumstances, for example, to accommodate increased print speeds. Increasing the temperature of the co-reactive components and/or the co-reactive composition may also be used to adjust the viscosity to facilitate mixing the co-reactive components and/or depositing the co-reactive composition.
The co-reactive composition may include a co-reactive compound capable of co-reacting at a temperature of less than 50 ℃ without exposure to actinic radiation and may optionally include a catalyst.
For example, the co-reactive composition may include compounds such as monomers and/or prepolymers that include co-reactive functional groups including, for example, any of those disclosed herein.
The co-reactive composition may further comprise a suitable catalyst or combination of catalysts for catalyzing the reaction between the co-reactive compounds.
The co-reactive composition may be an actinic radiation curable co-reactive composition, wherein the curing reaction between the co-reactive compounds in the co-reactive composition is initiated by exposing the co-reactive composition to actinic radiation.
Actinic radiation includes alphSup>A-rays, gammSup>A-rays, X-rays, ultraviolet (UV) radiation (200 nm to 400 nm), such as UV-A radiation (320 nm to 400 nm), UV-B radiation (280 nm to 320 nm) and UV-C radiation (200 nm to 280 nm); visible radiation (400 nm to 770 nm), radiation in the blue wavelength range (450 nm to 490 nm), infrared radiation (> 700 nm), near infrared radiation (0.75 μm to 1.4 μm) and electron beams.
The radiation curable co-reactive composition may comprise compounds that are capable of co-reacting by a free radical mechanism. Examples of free radical curing reactions include thiol/alkenyl reactions and thiol/alkynyl reactions.
The radiation curable co-reactive composition may include any suitable free radical polymerization initiator or combination of suitable free radical polymerization initiators. Examples of the radical polymerization initiator include photoinitiators, heat-activated radical generators, cationic radical generators, and dark-curing radical generators.
The radiation curable co-reactive composition may include a photoinitiator, such as a visible light initiator or a UV photoinitiator.
The radiation curable co-reactive composition may include a heat activated radical generator.
The radiation curable co-reactive composition may include a cationic free radical generator.
The radiation curable co-reactive composition may include a dark cure free radical generator.
The free radical photopolymerization may be initiated by exposing the coreactive composition to actinic radiation, e.g., UV radiation, for example, for less than 180 seconds, less than 120 seconds, less than 90 seconds, less than 60 seconds, less than 30 seconds, less than 15 seconds, or less than 5 seconds. The total power of the UV exposure may be, for example, 50mW/cm 2 To 500mW/cm 2 、50mW/cm 2 To 400mW/cm 2 、50mW/cm 2 To 300mW/cm 2 、100mW/cm 2 To 300mW/cm 2 Or 150mW/cm 2 To 250mW/cm 2 。
The actinic radiation curable co-reactive composition may be exposed to 1J/cm 2 To 4J/cm 2 To cure the composition. The UV source is an 8W lamp with UVA spectrum. Other dosages and/or other UV sources may be used. The UV dose for the curing composition may be, for example, 0.5J/cm 2 To 4J/cm 2 、0.5J/cm 2 To 3J/cm 2 、1J/cm 2 To 2J/cm 2 Or 1J/cm 2 To 1.5J/cm 2 。
The actinic radiation curable co-reactive compositions may also be cured with radiation in the blue wavelength range, for example using light emitting diodes.
Examples of actinic radiation curable sealant compositions suitable for use in sealing caps are disclosed, for example, in U.S. patent No. 8,729,198; U.S. patent No. 8,729,198; U.S. patent No. 9,533,798; U.S. patent No. 10,233,369; U.S. application publication No. 2019/0169465; PCT international publication No. PCT/US2018/36746; U.S. application publication No. 2018/0215974; and U.S. patent No. 7,438,974.
The free radically polymerizable co-reactive composition may be transmissive to actinic radiation such that incident actinic radiation may generate sufficient free radicals to allow the free radically polymerizable co-reactive composition to fully cure.
For example, the actinic radiation transmissive co-reactive composition may transmit actinic radiation through a thickness of the co-reactive composition, such as from 1mm to 30mm, from 1mm to 25mm, from 1mm to 20mm, from 1mm to 15mm, or from 1mm to 10mm.
The free radically polymerizable co-reactive composition may be partially transmissive to actinic radiation such that incident actinic radiation may generate sufficient free radicals to initiate free radical polymerization of the co-reactive composition in at least a portion of the exposed co-reactive composition. The unexposed portion of the coreactive composition may be cured by another free radical mechanism, such as a dark cure mechanism, or may be cured by a non-free radical mechanism.
The free radical initiation wavelength range may depend on the type of free radical generator in the co-reactive composition.
The first co-reactive composition may have the same cure rate as the second co-reactive composition or may have a different cure rate than the second co-reactive composition. For example, for ease of handling, the first co-reactive composition used to make the sealing cap may have a faster cure rate than the second co-reactive composition. The cure rate of the co-reactive composition may be selected to enhance one or more properties of the inner and outer portions of the sealing cap.
Using coreactive three-dimensional printing, the coreactive composition may be deposited, for example, at a rate of 1 mm/sec to 400 mm/sec and/or at a flow rate of 0.1 mL/min to 20,000 mL/min.
The first and second coreactive compositions may be the same or different. For example, different co-reactive compositions may include differences in the types and amounts of ingredients, which may result in different portions of the sealing cap having different properties. For example, the co-reactive composition used to form the sealing cap may include reactants, catalysts, adhesion promoters, fillers, reactive diluents, colorants, rheology control agents, and/or photochromic agents, which may be the same or different or present at a different wt% or vol% than another layer of the multi-layer sealing cap. The co-reactive compositions may also include the same or different cure chemistries.
The co-reactive composition that is capable of curing without exposure to actinic radiation can be deposited and allowed to cure, and the rate of cure will be determined by, for example, the cure chemistry, type and amount of catalyst, temperature, and viscosity of the deposited co-reactive composition. After deposition, the coreactive composition may be exposed to heat to accelerate curing of at least a portion of the coreactive composition.
Curing of the free radically polymerizable co-reactive composition may be initiated by activating the free radical generator, for example by exposing the free radically polymerizable co-reactive composition to actinic radiation or heat.
For example, the free radically polymerizable co-reactive composition may be exposed to actinic radiation during deposition of the free radically polymerizable co-reactive composition and/or after the free radically polymerizable co-reactive composition has been deposited while the free radically polymerizable co-reactive composition is in the three-dimensional printing device. The deposited free radically polymerizable co-reactive composition may be exposed to actinic radiation, for example, after initial deposition of the co-reactive composition or after manufacture of the seal cap shell depending on the manufacturing method, after application of a continuous layer thereto as a fastener to form a seal cap or after application of the seal cap to a fastener.
The sealing cap may be manufactured using an actinic radiation curable co-reactive composition and/or the internal volume may comprise an actinic radiation curable co-reactive composition. The encapsulant sealing the cap and filling the interior volume may comprise a co-reactive composition that is not curable using actinic radiation. The shell may comprise an actinic radiation curable composition and the sealant filling the interior volume may comprise a non-actinic radiation curable co-reactive composition. The shell of the sealing cap may comprise a co-reactive composition that is not curable using actinic radiation, and the sealant filling the interior volume may comprise a co-reactive composition that is curable by actinic radiation.
The sealing cap can be manufactured by depositing successive layers of an actinic radiation curable co-reactive composition using three-dimensional printing.
The shell may also be exposed to actinic radiation after fabrication and prior to filling the interior volume with the actinic radiation curable co-reactive composition to partially cure the shell or to fully cure the shell. The shell may be at least partially cured to provide a retainer for the internal composition and to facilitate the ability to handle and assemble the sealing cap over the fastener.
When the shell is constructed, the physical properties of the co-reactive composition may be such that the deposited co-reactive composition retains its intended shape and has sufficient mechanical strength to support the upper layer of the co-reactive composition before the lower layer is fully cured. The physical properties may be determined in part by the amount of ingredients in the composition, as well as the type and rate of curing, and the like.
The sealing cap may be manufactured by printing a co-reactive composition that does not require exposure to actinic radiation to initiate a chemical reaction. The shell may be manufactured using three-dimensional printing to deposit successive layers of the co-reactive composition to form a sealed cap shell, and the interior volume may be filled with the same or different co-reactive composition. Procedures similar to those described for making actinic radiation curable sealing caps are applicable except that the coreactive composition is exposed to actinic radiation.
The shell may be at least partially cured while the second co-reactive composition is deposited within the interior volume. For example, the shell may have a non-stick surface or have a hardness of, for example, greater than shore 5A or greater than shore 10A when the second coreactive composition is deposited within the interior volume. The second co-reactive composition has a compound that can react with the compound in the first co-reactive composition to form a chemical bond, and only partial curing of the shell may be desired. The chemical bond between the shell and the inner sealant can improve the integrity and adhesive strength of the interface. The co-reactive compositions of adjacent layers may chemically and/or physically interact to form strong interlayer bonds. Interactions may be through chemical bonding and/or physical entanglement between adjacent layers.
An optional intermediate layer may be applied to the inner surface of the shell after the shell is manufactured and before the interior volume is filled. The intermediate layer may be used to promote adhesion between the shell and the second co-reactive composition, promote chemical bonding between the shell and the second co-reactive composition, and/or may be used to enhance properties such as chemical resistance. The intermediate layer may have a thickness of, for example, 0.05mm to 3mm, for example, 0.1mm to 2 mm. The intermediate layer may be applied to the inner surface of the shell after the shell is manufactured, or may be applied to the extruded first and/or second co-reactive compositions as the extrudate is deposited by a three-dimensional printing apparatus. For example, the adhesion promoting layer may be co-extruded with the extruded co-reactive composition, or the adhesion promoting layer may be applied to the extrudate by contacting at least a portion of the extrudate with the adhesion promoting composition prior to deposition of the extrudate onto the substrate or underlying layer of the deposited co-reactive composition.
After the shell has been manufactured, the interior volume defined by the shell may be at least partially filled with the second co-reactive composition. The amount of the second co-reactive composition deposited within the interior volume may be selected to minimize the amount of the second co-reactive composition that moves out of the sealing cap when the sealing cap is assembled onto the fastener. At the same time, the amount of the second co-reactive composition within the interior volume may be sufficient to facilitate the second co-reactive composition being able to fully conform to the geometry of the fastener and minimize the presence of voids when the sealing cap is assembled over the fastener.
As with the first co-reactive composition, the second co-reactive composition may comprise a one-part co-reactive composition or a multi-part composition deposited into the interior volume using three-dimensional printing (wherein two or more components of the actinic radiation curable co-reactive composition are combined in a mixer at the time of use and extruded into the interior volume through a nozzle using a three-dimensional printing apparatus). The method of filling the internal volume with the second actinic radiation curable composition may be designed to avoid entrainment of voids and air pockets.
After the interior volume of the shell is filled with the second co-reactive composition, and before the second co-reactive composition cures, a sealing cap may be assembled thereon as a fastener. At the time of assembly of the sealing cap over the fastener, it is desirable that the outer surface of the shell has been cured so that the sealing cap can be manually or automatically manipulated. For example, the shell may have a non-stick surface. For example, the shell may have sufficient mechanical strength that it can be picked up and placed onto the fastener with sufficient force so that the second co-reactive composition can conform to the geometry of the fastener to remove air pockets and minimize voids. The second co-reactive composition may have a viscosity such that the second co-reactive composition remains within the interior volume when the sealing cap is assembled over the fastener such that the second co-reactive composition does not flow out to a perceptible extent from under the base of the sealing cap when the sealing cap is manipulated over the fastener. Further, the second co-reactive composition may have a sufficiently low viscosity such that it conforms to the fastener and other elements of the sealed portion.
Any suitable photoinitiator may be used, such as a thermally activated radical initiator, or a radical initiator activated by actinic radiation, or a photoinitiator, or the like.
The photoinitiator may be activated by actinic radiation, which may apply energy, which upon irradiation is effective to generate initiating species from the photopolymerization initiator, such as alpha-rays, gamma-rays, X-rays, ultraviolet (UV) light, including UVA, UVA and UVC spectra), visible light, blue light, infrared, near infrared, or electron beams. For example, the photoinitiator may be a UV photoinitiator.
Examples of suitable UV photoinitiators include alpha-hydroxy ketone, benzophenone, alpha-diethoxyacetophenone, 4-diethylaminobenzophenone, 2-dimethoxy-2-phenylacetophenone, 4-isopropylphenyl 2-hydroxy-2-propyl ketone, 1-hydroxycyclohexylphenyl ketone, isoamyl p-dimethylaminobenzoate, methyl 4-dimethylaminobenzoate, methyl O-benzoyl benzoate, benzoin diethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-isopropylthioxanthone, dibenzosuberone, 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide, dicyclophosphine oxide, benzophenone photoinitiators, oxime photoinitiators, phosphine oxide photoinitiators, and combinations of any of the foregoing.
The heat-activated radical initiator may become active at high temperatures, for example at temperatures above 25 ℃. Examples of suitable heat-activated free radical initiators include organic peroxy compounds, azobis (organonitrile) compounds, N-acyloxyamine compounds, O-imino-isourea compounds, and combinations of any of the foregoing. Examples of suitable organic peroxy compounds that may be used as thermal polymerization initiators include peroxymonocarbonates, such as t-butyl peroxy 2-ethylhexyl carbonate and t-butyl peroxy isopropyl carbonate; peroxyketals, such as 1, 1-di- (tert-butylperoxy) -3, 5-trimethylcyclohexane; peroxydicarbonates, such as di (2-ethylhexyl) peroxydicarbonate, di (sec-butyl) peroxydicarbonate and diisopropyl peroxydicarbonate; diacyl peroxides such as 2, 4-dichlorobenzoyl peroxide, isobutyryl peroxide, decanoyl peroxide, lauroyl peroxide, propionyl peroxide, acetyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide; peroxyesters, such as t-butyl peroxypivalate, t-butyl peroxyoctoate, and t-butyl peroxyisobutyrate; methyl ethyl ketone peroxide, acetyl cyclohexane sulfonyl peroxide, and combinations of any of the foregoing. Other examples of suitable thermal polymerization initiators include 2, 5-dimethyl-2, 5-di (2-ethylhexanoyl peroxide) hexane and/or 1, 1-bis (t-butylperoxy) -3, 5-trimethylcyclohexane. Examples of suitable azobis (organic nitrile) compounds that may be used as thermal polymerization initiators include azobis (isobutyronitrile), 2' -azobis (2-methyl-butyronitrile), and/or azobis (2/1-dimethylvaleronitrile).
The coreactant composition may have a tack free time of less than 8 hours, less than 6 hours, less than 4 hours, less than 2 hours, less than 1 hour, or less than 30 minutes at 25C/50% RH, wherein the tack free time is determined according to AS5127/1 (5.8) (aerospace standard test method for aerospace sealants).
The co-reactive composition used to form the sealing cap exhibiting a fast shore 10A hardness time may include, for example, co-reactants having a fast cure chemistry, a system curable by actinic radiation, a catalyst, and combinations of any of the foregoing.
The cured composition may have a fast shore 10A hardness time of less than 10 minutes, wherein the hardness is determined according to ISO 868 at 23 ℃/55% RH.
The co-reactive composition used to form the seal cap with electrical conductivity, EMI/RFI shielding, and/or static dissipation may include, for example, an electrically conductive filler or a combination of electrically conductive fillers.
The co-reactive composition may be substantially free of solvent. For example, the co-reactive composition may have less than 5wt%, less than 2wt%, less than 1wt%, less than 0.5wt%, or less than 0.1wt% solvent, wherein wt% is based on the total weight of the co-reactive composition.
The co-reactive composition may include, for example, one or more additives such as, for example, catalysts, polymerization initiators, adhesion promoters, reactive diluents, plasticizers, fillers, colorants, photochromic agents, rheology modifiers, reactive diluents, curing activators and promoters, corrosion inhibitors, flame retardants, UV stabilizers, rain erosion inhibitors, or a combination of any of the foregoing.
The co-reactive composition may include a catalyst or combination of catalysts, wherein one or more catalysts are selected to catalyze a reaction between co-reactants in the co-reactive composition, such as a first co-reactive compound and a second co-reactive compound.
The catalyst or combination of catalysts may be selected to catalyze the reaction of the coreactants in the coreactant composition, such as the reaction of the first compound and the second compound. Suitable catalysts will depend on the cure chemistry. For example, a thiol-ene or thiol epoxide can include an amine catalyst.
The co-reactive composition may include, for example, 0.1wt% to 1wt%, 0.2wt% to 0.9wt%, 0.3wt% to 0.7wt%, or 0.4wt% to 0.6wt% of the catalyst or combination of catalysts, wherein wt% is based on the total weight of the co-reactive composition.
The catalyst may comprise a latent catalyst or a combination of latent catalysts. Latent catalysts comprise catalysts that have little or no activity prior to release or activation, e.g., by physical and/or chemical mechanisms. The latent catalyst may be contained within the structure or may be chemically blocked. The controlled release catalyst may release the catalyst upon exposure to ultraviolet radiation, heat, sonication, or moisture. The latent catalyst may be sequestered within a core-shell structure or entrapped within a matrix of crystalline or semi-crystalline polymer, wherein the catalyst may diffuse from the encapsulant over time or upon activation, such as by application of thermal or mechanical energy.
The co-reactive composition may include a dark cure catalyst or a combination of dark cure catalysts. Dark cure catalysts refer to catalysts that are capable of generating free radicals without exposure to electromagnetic energy.
The dark cure catalyst comprises, for example, a combination of a metal complex and an organic peroxide, a trialkylborane complex and a peroxide-amine redox initiator. The dark cure catalyst may be used in combination with the photopolymerization initiator or independently of the photopolymerization initiator.
The co-reactive composition based on thiol/thiol curing chemistry may include a curing activator or combination of curing activators to initiate thiol/thiol polymerization reactions. The curing activator may be used, for example, in a co-reactive composition wherein the first compound and the second compound comprise a thiol-terminated sulfur-containing prepolymer, such as a thiol-terminated polysulfide prepolymer.
The curing activator may include an oxidizing agent capable of oxidizing thiol groups to form disulfide bonds. Examples of suitable oxidizing agents include lead dioxide, manganese dioxide, calcium dioxide, sodium perborate monohydrate, calcium peroxide, zinc peroxide, and dichromate.
The curing activator may include an inorganic activator, an organic activator, or a combination thereof.
Examples of suitable inorganic activators include metal oxides. Examples of suitable metal oxide activators include zinc oxide (ZnO), lead oxide (PbO), lead peroxide (PbO) 3 ) Manganese dioxide (MnO) 2 ) Sodium perborate (NaBO) 3 ·H 2 O), potassium permanganate (KMnO) 4 ) Calcium peroxide (CaCO) 3 ) Barium peroxide (BaO) 3 ) Cumene hydroperoxide and combinations of any of the foregoing. The curing activator may be MnO 2 。
The co-reactive composition based on thiol/thiol curing chemistry may include, for example, 1wt% to 10wt% of a curing activator or combination of curing activators, where wt% is based on the total weight of the composition. For example, the co-reactive composition may include from 1wt% to 9wt%, from 2wt% to 8wt%, from 3wt% to 7wt%, or from 4wt% to 6wt% of an activator or combination of curing activators, wherein wt% is based on the total weight of the composition. For example, the co-reactive composition may include greater than 1wt% of a curing activator or combination of curing activators, greater than 2wt%, greater than 3wt%, greater than 4wt%, greater than 5wt% or greater than 6wt% of a curing activator or combination of curing activators, wherein wt% is based on the total weight of the composition.
The co-reactive composition based on thiol/thiol curing chemistry may comprise a curing accelerator or a combination of curing accelerators.
The cure accelerator can act as a sulfur donor to produce reactive sulfur fragments capable of reacting with the thiol groups of the thiol-terminated polysulfide prepolymer.
Examples of suitable cure accelerators include thiazoles, thiurams, sulfenamides, guanidines, dithiocarbamates, xanthates, thioureas, aldamines, and combinations of any of the foregoing.
The cure accelerator may be a thiuram polysulfide, a thiuram disulfide, or a combination thereof.
Examples of other suitable cure accelerators also include triazines and sulfides or metals and amine salts of dialkyldithiophosphoric acids and dithiophosphoric esters, such as triazines and sulfides or metals and amine salts of dialkyldithiophosphoric acids, and combinations of any of the foregoing. Examples of non-sulfur-containing cure accelerators include Tetramethylguanidine (TMG), di-o-tolylguanidine (DOTG), sodium hydroxide (NaOH), water, and a base.
The co-reactive composition may comprise, for example, 0.01wt% to 2wt% of a cure accelerator or combination of cure accelerators, 0.05wt% to 1.8wt%, 0.1wt% to 1.6wt%, or 0.5wt% to 1.5wt% of a cure accelerator or combination of cure accelerators, wherein wt% is based on the total weight of the composition. The co-reactive composition may include, for example, less than 2wt%, less than 1.8wt%, less than 1.6wt%, less than 1.4wt%, less than 1.2wt%, less than 1wt%, less than 0.5wt%, less than 0.1wt%, or less than 0.05wt% of a curing accelerator or combination of curing accelerators, wherein the wt% is based on the total weight of the composition.
The coreactive composition may include an adhesion promoter or a combination of adhesion promoters. The adhesion promoter may enhance adhesion of the coreactive composition to an underlying substrate such as a metal, composite, polymer, or ceramic surface, or to a coating such as a primer coating or other coating. The adhesion promoter may enhance adhesion to the filler and to other layers of the sealing cap.
The adhesion promoter may comprise a phenolic adhesion promoter, a combination of phenolic adhesion promoters, an organofunctional silane, a combination of organofunctional silanes, or a combination of any of the foregoing. The organofunctional alkoxysilane may be an amine functional alkoxysilane. The organic group may be selected from, for example, a thiol group, an amine group, a hydroxyl group, an epoxy group, an alkynyl group, an alkenyl group, an isocyanate group, or a michael acceptor group.
The phenolic adhesion promoter may include a cooked phenolic resin, an uncooked phenolic resin, or a combination thereof. Examples of suitable adhesion promoters include phenolic resins, e.gPhenol resins, and organosilanes, e.g. epoxy-, mercapto-or amine-functional silanes, e.g +.>An organosilane. By cooked phenol resin is meant a phenol resin that has been co-reacted with monomers, oligomers and/or prepolymers.
The phenolic adhesion promoter may comprise the reaction product of a condensation reaction of a phenolic resin with one or more thiol-terminated polysulfides. The phenolic adhesion promoter may be thiol-terminated.
Examples of suitable phenolic resins include those synthesized from 2- (hydroxymethyl) phenol, (4-hydroxy-1, 3-phenylene) dimethanol, (2-hydroxybenzene-1, 3, 4-triyl) dimethanol, 2-benzyl-6- (hydroxymethyl) phenol, (4-hydroxy-5- ((2-hydroxy-5- (hydroxymethyl) cyclohex-2, 4-dien-1-yl) methyl) -1, 3-phenylene) dimethanol, (4-hydroxy-5- ((2-hydroxy-3, 5-bis (hydroxymethyl) cyclohex-2, 4-dien-1-yl) methyl) -1, 3-phenylene) dimethanol, and combinations of any of the foregoing. Suitable phenolic resins may be synthesized by the base catalyzed reaction of phenol with formaldehyde. Phenolic adhesion promoters may include those available from Durez CorporationResin, & gt>Resin or->Resin and (e.g.)>Reaction products of condensation reactions of thiol-terminated polysulfides such as resins. />Examples of resins include->75108 (allyl ether of methylol phenol, see U.S. Pat. No. 3,517,082) and +.>75202。/>Examples of resins include->29101、/>29108、/>29112、/>29116、/>29008、/>29202、/>29401、/>29159、/>29181、/>92600、/>94635、/>94879 and->94917。/>One example of a resin is34071。
The co-reactive composition may include an organofunctional alkoxysilane adhesion promoter, such as an organofunctional alkoxysilane. The organofunctional alkoxysilane may include a hydrolyzable group bonded to a silicon atom and at least one organofunctional group. The organofunctional alkoxysilane may have the structure R a -(CH 2 ) n -Si(-OR) 3-n R n Wherein R is a Is an organofunctional group, n is 0, 1 or 2, and R is an alkyl group, such as methyl or ethyl. Examples of organic functional groups include epoxy, amino, methacryloxy, or sulfide groups. The organofunctional alkoxysilane may be a dual-arm alkoxysilane having two or more alkoxysilane groups, a functional dual-arm alkoxysilane, a non-functional dual-arm alkoxysilane, or a combination of any of the foregoing. The organofunctional alkoxysilane may be a combination of mono-and di-arm alkoxysilanes.
Examples of suitable amino-functional alkoxysilanes under the trade name include->A-1100 (gamma-aminopropyl triethoxysilane), a>A-1108 (gamma-aminopropyl silsesquioxane), a method of preparing the same>A-1110 (gamma-aminopropyl trimethoxysilane), -, a>1120 (N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane), -/->1128 (benzylamino-silane), +.>A-1130 (Triamino-functional silane), -, and->Y-11699 (bis- (gamma-triethoxysilylpropyl) amine), - (Y-O-R)>A-1170 (bis- (gamma-trimethoxysilylpropyl) amine), -a-1170 (gamma-trimethoxysilylpropyl)>A-1387 (Polyamide), -/->Y-19139 (ethoxy Polyamide) anda-2120 (N- β - (aminoethyl) - γ -aminopropyl methyldimethoxysilane). Suitable amine functional alkoxysilanes are commercially available from, for example, gelest Inc, dow Corning Corporation and Mom entive Performance Materials,Inc。
The co-reactive composition may include a filler or a combination of different fillers. The filler may include, for example, an inorganic filler, an organic filler, a low density filler, a conductive filler, or a combination of any of the foregoing.
The co-reactive composition used to form the multi-layer sealing cap may include an inorganic filler or a combination of inorganic fillers.
Inorganic fillers may be included to provide mechanical reinforcement and control of rheological properties of the composition, such as viscosity. Inorganic fillers may be added to the composition to impart desired physical properties such as, for example, to increase impact strength, control viscosity, and/or alter the electrical properties of the cured composition.
Inorganic fillers that may be used in the co-reactive composition include carbon black, calcium carbonate, precipitated calcium carbonate, calcium hydroxide, hydrated alumina (aluminum hydroxide), talc, mica, titanium dioxide, aluminum silicate, carbonates, chalk, silicates, glass, metal oxides, graphite, and combinations of any of the foregoing.
Suitable calcium carbonate fillers may include those available from Solvay Special Chemicals as31、312、/>U1S1、/>UaS2、/>N2R、/>SPM and->SPT, etc. The calcium carbonate filler may comprise a combination of precipitated calcium carbonate.
The inorganic filler may be surface treated to provide a hydrophobic or hydrophilic surface, which may facilitate dispersion and compatibility of the inorganic filler with other components of the coreactive composition. The inorganic filler may comprise surface modified particles, such as surface modified silica. The surface of the silica particles may be modified, for example, to adjust the hydrophobicity or hydrophilicity of the surface of the silica particles. Surface modification can affect the dispensability, viscosity, cure rate, and/or adhesion of the particles.
The co-reactive composition may include an organic filler or a combination of organic fillers.
The organic filler may be selected to have a low specific gravity and resistance to solvents such as JRF type I and/or to reduce the density of the sealant layer. Suitable organic fillers may also have acceptable adhesion to sulfur-containing polymer substrates. The organic filler may comprise solid powders or particles, hollow powders or particles, or a combination thereof.
The organic filler may have a specific gravity of, for example, less than 1.15, less than 1.1, less than 1.05, less than 1, less than 0.95, less than 0.9, less than 0.8, or less than 0.7. The organic filler may have a specific gravity in the range of, for example, 0.85 to 1.15, 0.9 to 1.1, 0.9 to 1.05, or 0.85 to 1.05.
The organic filler may include, for example, a thermoplastic, a thermoset, or a combination thereof. Examples of suitable thermoplastics and thermosets include epoxy resins, epoxy amides, ETFE copolymers, nylons, polyethylenes, polypropylenes, polyethylene oxides, polypropylene oxides, polyvinylidene chloride, polyvinyl fluorides, TFE, polyamides, polyimides, ethylene propylene, perfluorohydrocarbons, fluoroethylenes, polycarbonates, polyetheretherketones, polyetherketones, polyphenylene oxides, polyphenylene sulfides, polystyrene, polyvinyl chloride, melamine, polyesters, phenolic resins, epichlorohydrins, fluorinated hydrocarbons, polycyclic compounds, polybutadiene, polychloroprene, polyisoprene, polysulfides, polyurethanes, isobutylene isoprene, silicones, styrene butadiene, liquid crystal polymers, or combinations of any of the foregoing.
Examples of suitable polyamide 6 and polyamide 12 particles are available from Toray Plastics at stages SP-500, SP-10, TR-1 and TR-2. Suitable polyamide powders are also available under the trade namePurchased from Arkema Group and under the trade name +.>Purchased from Evonik Industries.
The organic filler may have any suitable shape. For example, the organic filler may include portions of the crushed polymer that have been filtered to select a desired size range. The organic filler may comprise substantially spherical particles. The particles may be solid or porous.
The organic filler may have a number average particle diameter in the range of, for example, 1 μm to 100 μm, 2 μm to 40 μm, 2 μm to 30 μm, 4 μm to 25 μm, 4 μm to 20 μm, 2 μm to 12 μm, or 5 μm to 15 μm. The organic filler may have a number average particle size of, for example, less than 100 μm, less than 75 μm, less than 50 μm, less than 40 μm, or less than 20 μm. The particle size distribution may be determined using a fischer particle meter or by optical inspection.
The co-reactive composition used to form the sealing cap exhibiting low density may include, for example, a low density filler such as a low density organic filler, hollow microspheres, coated microspheres, or a combination of any of the foregoing.
The sealing cap may exhibit a specific gravity of, for example, less than 1.1, less than 1.0, less than 0.9, less than 0.8 or less than 0.7, wherein the specific gravity is determined according to ISO 2781 at 23 ℃/55% RH.
The organic filler may comprise a low density, for example modified expanded thermoplastic microcapsules. Suitable modified expanded thermoplastic microcapsules may comprise an outer coating of melamine or urea/formaldehyde resin. The coreactant composition may comprise a low density microcapsule. The low density microcapsules may comprise thermally expandable microcapsules.
Thermally expandable microcapsules refer to hollow shells comprising volatile materials that expand at a predetermined temperature. The number average primary particle size of the thermally expandable thermoplastic microcapsules may be 5 μm to 70 μm, in some cases 10 μm to 24 μm or 10 μm to 17 μm. The term "average primary particle size" refers to the average particle size (a digitally weighted average of the particle size distribution) of the microcapsules prior to any expansion. The particle size distribution may be determined using a fischer particle meter or by optical inspection.
Examples of materials suitable for forming the walls of the thermally expandable microcapsules include vinylidene chloride, acrylonitrile, styrene, polycarbonate, polymers of methyl methacrylate, ethyl acrylate, and vinyl acetate, copolymers of these monomers, and combinations of polymers and copolymers. The cross-linking agent may be included in the material forming the walls of the thermally expandable microcapsules.
Examples of suitable thermoplastic microcapsules include Expancel available from akzo nobel TM Microcapsules, e.g.DE microsphere. Suitable Expancel TM Examples of DE microspheres include->920DE 40920DE 80. Suitable low density microcapsules are also available from Kureha Corporation.
The low density filler, such as low density microcapsules, may be characterized by a specific gravity in the range of 0.01 to 0.09, 0.04 to 0.08, 0.01 to 0.07, 0.02 to 0.06, 0.03 to 0.05, 0.05 to 0.09, 0.06 to 0.09, or 0.07 to 0.09, wherein the specific gravity is determined according to ISO 787-11. Low density fillers, such as low density microcapsules, may be characterized by a specific gravity of less than 0.1, less than 0.09, less than 0.08, less than 0.07, less than 0.06, less than 0.05, less than 0.04, less than 0.03, or less than 0.02, wherein the specific gravity is determined according to a ISO 787-11.
Low density fillers, such as low microcapsules, may be characterized by a number average particle size of, for example, 1 μm to 100 μm, and may have a substantially spherical shape. Low density fillers such as low density microcapsules may be characterized by, for example, an average particle size of 10 μm to 100 μm, 10 μm to 60 μm, 10 μm to 40 μm, or 10 μm to 30 μm, as determined according to ASTM D6913
Low density fillers such as low density microcapsules may include expanded microcapsules or microspheres having a coating of an aminoplast resin such as melamine resin. Aminoplast resin coated particles are described, for example, in U.S. patent No. 8,993,691. Such microcapsules may be formed by heating microcapsules comprising a blowing agent surrounded by a thermoplastic shell. The uncoated low density microcapsules may be reacted with an aminoplast resin such as urea/formaldehyde resin to provide a coating of thermosetting resin on the outer surface of the particles.
The coating with aminoplast resin may be characterized by a specific gravity, for example, in the range of 0.02 to 0.08, in the range of 0.02 to 0.07, in the range of 0.02 to 0.06, in the range of 0.03 to 0.07, in the range of 0.03 to 0.065, in the range of 0.04 to 0.065, in the range of 0.045 to 0.06, or in the range of 0.05 to 0.06, wherein the specific gravity is determined according to ISO 787-11.
The co-reactive composition may comprise a micronized oxidized polyethylene homopolymer. The organic filler may comprise polyethylene, such as oxidized polyethylene powder. Suitable polyethylenes are available, for example, under the trade namePurchased from Honeywell International, inc under the trade name +.>Purchased from INEOS under the trade name +. >Purchased from Mitsui Chemicals America, inc.
The co-reactive composition may include, for example, 1wt% to 90wt% low density filler, 1wt% to 60wt%, 1wt% to 40wt%, 1wt% to 20wt%, 1wt% to 10wt%, or 1wt% to 5wt% low density filler, where wt% is based on the total weight of the composition.
The co-reactive composition may include greater than 1wt% low density filler, greater than 1wt%, greater than 2wt%, greater than 3wt%, greater than 4wt%, greater than 1wt% or greater than 10wt% low density filler, wherein wt% is based on the total weight of the composition.
The co-reactive composition may include 1 to 90vol% low density filler, 5 to 70vol%, 10 to 60vol%, 20 to 50vol% or 30 to 40vol% low density filler, wherein vol% is based on the total volume of the co-reactive composition.
The co-reactive composition may include greater than 0.5vol% low density filler, greater than 1vol%, greater than 5vol%, greater than 10vol%, greater than 20vol%, greater than 30vol%, greater than 40vol%, greater than 50vol%, greater than 60vol%, greater than 70vol%, or greater than 80vol% low density filler, wherein vol% is based on the total volume of the co-reactive composition.
The coreactive composition may comprise a conductive filler or a combination of conductive fillers. The conductive filler may comprise an electrically conductive filler, a semi-conductive filler, a thermally conductive filler, a magnetic filler, an EMI/RFI shielding filler, an electrostatic dissipative filler, an electroactive filler, or a combination of any of the foregoing.
Examples of suitable conductive fillers such as conductive fillers include metals, metal alloys, conductive oxides, semiconductors, carbon fibers, and combinations of any of the foregoing.
Other examples of conductive fillers include conductive noble metal-based fillers, such as pure silver; noble metal plated noble metals, such as silver-plated gold; noble metal plated non-noble metals such as silver plated copper, nickel or aluminum, such as silver plated aluminum core particles or platinum plated copper particles; noble metal plated glass, plastic or ceramic, such as silver plated glass microspheres, noble metal plated aluminum or noble metal plated plastic microspheres; noble metal plated mica; and other such noble metal conductive fillers. Non-noble metal based materials may also be used and comprise non-noble metals such as non-noble metal plated, for example copper coated iron particles or nickel plated copper; non-noble metals such as copper, aluminum, nickel, cobalt; non-noble metal plated non-metals, such as nickel plated graphite and non-metallic materials, such as carbon black and graphite. The combination of conductive fillers and the shape of the conductive fillers may be used to achieve the desired conductivity, EMI/RFI shielding effectiveness, hardness, and other properties suitable for a particular application.
The amount and type of conductive filler can be selected to produce a composition that exhibits less than 0.50 Ω/cm when cured 2 Sheet resistance (four-point resistance) of less than 0.15 Ω/cm 2 Is described. The amount and type of filler may also be selected to provide effective EMI/RFI shielding for the aperture sealed with the co-reactive composition over a frequency range of 1MHz to 18 GHz.
The organic filler, inorganic filler, and low density filler may be coated with a metal to provide a conductive filler.
The conductive filler may comprise graphene. Graphene comprises a dense honeycomb lattice of carbon atoms having a thickness equal to the atomic size of one carbon atom, i.e., a monolayer sp arranged in a two-dimensional lattice 2 And (3) hybridizing carbon atoms.
The conductive filler may comprise a magnetic filler or a combination of magnetic fillers.
The magnetic filler may comprise a soft magnetic metal. This can enhance the magnetic permeability of the magnetic molding resin. As the main component of the soft magnetic metal, at least one magnetic material selected from Fe, fe-Co, fe-Ni, fe-Al, and Fe-Si may be used. The magnetic filler may be a soft magnetic metal having a high bulk permeability. As the soft magnetic metal, at least one magnetic material of Fe, feCo, feNi, feAl and FeSi can be used. Specific examples include permalloy (FeNi alloy), super permalloy (FeNiMo alloy), sendust (fesai alloy), feSi alloy, feCo alloy, feCr alloy, feCrSi alloy, feNiCo alloy, and Fe. Other examples of magnetic fillers include iron-based powders, iron-nickel-based powders, iron powders, ferrite powders, alnico powders, sm 2 Co 17 Powder, nd-B-Fe powder, barium ferrite BaFe 2 O 4 Bismuth ferrite BiFeO 3 Chromium dioxide CrO 2 SmFeN, ndFeB and SmCo.
The coreactive composition may include a hydroxy-functional vinyl ether or a combination of hydroxy-functional vinyl ethers. Reactive diluents may be used to reduce the viscosity of the composition. The reactive diluent may be a low molecular weight compound, for example having a molecular weight of less than 400Da, having at least one functional group capable of reacting with at least one reactant of the composition and becoming part of a crosslinked network. The reactive diluent may have, for example, one functional group or two functional groups. Reactive diluents may be used to control the viscosity of the composition or to improve wetting of the filler in the co-reactive composition.
The hydroxy-functional vinyl ether as reactive diluent may have the structure of formula (12):
CH 2 ＝CH-O-(CH 2 ) t -OH (12)
wherein t is an integer from 2 to 10. In the hydroxy-functional vinyl ether of formula (12), t may be 1, 2, 3, 4, 5, or t may be 6. Examples of suitable hydroxy-functional vinyl ethers include 1-methyl-3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, and combinations thereof. The hydroxy-functional vinyl ether may be 4-hydroxybutyl vinyl ether.
The co-reactive composition may include, for example, 0.1wt% to 10wt% of the hydroxy-functional vinyl ether, 0.2wt% to 9wt%, 0.3wt% to 0.7wt%, and 0.4wt% to 0.7wt%, where wt% is based on the total weight of the curable composition.
The co-reactive composition may include an amino-functional vinyl ether or a combination of amino-functional vinyl ethers as a reactive diluent.
The amino-functional vinyl ether as reactive diluent may have the structure of formula (13):
CH 2 ＝CH-O-(CH 2 ) w -NH 2 (13)
wherein w is an integer from 2 to 10. In the amino-functional vinyl ether of formula (13), w may be 1, 2, 3, 4, 5, or t may be 6. Examples of suitable amino-functional vinyl ethers include 1-methyl-3-aminopropyl vinyl ether, 4-aminobutyl vinyl ether, and combinations of any of the foregoing. The amino-functional vinyl ether may be 4-aminobutyl vinyl ether as a reactive diluent.
The co-reactive composition may include, for example, 0.1wt% to 10wt% of the amino-functional vinyl ether, 0.2wt% to 9wt%, 0.3wt% to 0.7wt%, and 0.4wt% to 0.7wt%, where the wt% is based on the total weight of the co-reactive composition.
The co-reactive composition may include vinyl diluents such as styrene, alpha-methylstyrene and para-vinyltoluene; vinyl acetate; and/or n-vinylpyrrolidone as reactive diluent.
The coreactive composition may contain a plasticizer or a combination of plasticizers. Plasticizers may be included to adjust the viscosity of the composition and to facilitate application.
Examples of suitable plasticizers include phthalates, terephthalic acid, isophthalic acid, hydrogenated terphenyl, tetrabiphenyl, and higher biphenyl or polybiphenyl, phthalates, chlorinated paraffins, modified polybiphenyl, tung oil, benzoates, dibenzoates, thermoplastic polyurethane plasticizers, phthalates, naphthalene sulfonates, trimellitates, adipates, sebacates, maleates, sulfonamides, organophosphates, polybutenes, butyl acetate, butyl cellosolve, butyl carbitol acetate, dipentene, tributyl phosphate, cetyl alcohol, diallyl phthalate, sucrose acetate isobutyrate, isooctyl epoxy resin acid, benzophenone, and combinations of any of the foregoing.
The co-reactive composition may comprise, for example, 0.5wt% to 7wt% of a plasticizer or combination of plasticizers, 1wt% to 6wt%, 2wt% to 5wt%, or 2wt% to 4wt% of a plasticizer or combination of plasticizers, wherein the wt% is based on the total weight of the co-reactive composition.
The co-reactive composition may include, for example, less than 8wt% plasticizer, less than 6wt%, less than 4wt%, or less than 2wt% plasticizer, or combination of plasticizers, wherein wt% is based on the total weight of the co-reactive composition.
The co-reactive composition may include a photochromic agent that is sensitive to the extent of cure or exposure to actinic radiation. The cure indicator may change color upon exposure to actinic radiation, which may be permanent or reversible. The cure indicator may be initially transparent and become colored upon exposure to actinic radiation, or may be initially colored and become transparent upon exposure to actinic radiation.
The co-reactive compositions provided by the present disclosure may include a corrosion inhibitor or a combination of corrosion inhibitors.
Examples of suitable corrosion inhibitors include zinc phosphate based corrosion inhibitors, lithium silicate corrosion inhibitors, such as lithium orthosilicate (Li 4 SiO 4 ) And lithium metasilicate (Li) 2 SiO 3 ) MgO, azoles, monomeric amino acids, dimeric amino acids, oligomeric amino acids, nitrogen-containing heterocyclic compounds, such as oxazoles, thiazoles, thiazolines, imidazoles, diazoles, pyridines, indolizines and triazines, tetrazoles and/or tolyltriazoles, corrosion-resistant particles, for example particles of inorganic oxides, including, for example, zinc oxide (ZnO), magnesium oxide (MgO), cerium oxide (CeO) 2 ) Molybdenum oxide (MoO) 3 ) And/or silicon dioxide (SiO) 2 ) And combinations of any of the foregoing.
The co-reactive composition may include less than 5wt% of a corrosion inhibitor or combination of corrosion inhibitors, less than 3wt%, less than 2wt%, less than 1wt%, or less than 0.5wt% of a corrosion inhibitor or combination of corrosion inhibitors, wherein the wt% is based on the total weight of the co-reactive composition.
The co-reactive composition may include a flame retardant or a combination of flame retardants.
The flame retardant may comprise an inorganic flame retardant, an organic flame retardant, or a combination thereof.
Examples of suitable inorganic flame retardants include aluminum hydroxide, magnesium hydroxide, zinc borate, antimony oxide, hydromagnesite, aluminum hydroxide (ATH), calcium phosphate, titanium oxide, zinc oxide, magnesium carbonate, barium sulfate, barium borate, kaolinite, silica, antimony oxide, and combinations of any of the foregoing.
Examples of suitable organic flame retardants include halogen-containing hydrocarbons, halogenated esters, halogenated ethers, chlorinated and/or brominated flame retardants, halogen-free compounds such as organic phosphorus compounds, organic nitrogen compounds, and the like, and combinations of any of the foregoing.
The co-reactive composition may include, for example, 1wt% to 30wt%, such as 1wt% to 20wt%, or 1wt% to 10wt% of a flame retardant or combination of flame retardants, based on the total weight of the co-reactive composition. For example, the co-reactive composition may include less than 30wt%, less than 20wt%, less than 10wt%, less than 5wt%, or less than 2wt% of a flame retardant or combination of flame retardants, based on the total weight of the co-reactive composition.
The co-reactive composition may include a moisture control additive or a combination of moisture control additives.
Examples of suitable moisture control additives include synthetic zeolite, activated alumina, silica gel, calcium oxide, magnesium oxide, molecular sieves, anhydrous sodium sulfate, anhydrous magnesium sulfate, alkoxysilanes, and combinations of any of the foregoing.
The co-reactive composition may include less than 5wt% moisture control additive or combination of moisture control additives, less than 3wt%, less than 2wt%, less than 1wt% or less than 0.5wt% moisture control additive or combination of moisture control additives, wherein wt% is based on the total weight of the co-reactive composition.
The co-reactive composition may include a UV stabilizer or a combination of UV stabilizers. The UV stabilizer comprises a UV absorber and a hindered amine light stabilizer. Examples of suitable UV stabilizers include those sold under the trade name(Solvay)、/>(BASF) and->(BASF) product.
The layers of the sealing cap may be designed to optimize certain desired properties, such as including chemical resistance, corrosion resistance, hydrolytic stability, low temperature flexibility, high temperature resistance, and/or the ability to dissipate electrical charges. The material forming the layers of the sealing cap, such as the sealing cap shell, the material filling the interior, and/or the material of the other layers may be selected to optimize one or more desired properties.
For example, the layer exhibiting low temperature flexibility may include a prepolymer, such as silicone, polytetrafluoroethylene, polythioether, polysulfide, polyformal, polybutadiene, certain elastomers, and combinations of any of the foregoing.
The layer exhibiting hydrolytic stability may comprise, for example, a prepolymer, such as silicone, polytetrafluoroethylene, polythioether, polysulfide, polyformal, polybutadiene, certain elastomers, and combinations of any of the foregoing, or a composition having a high crosslink density and/or may comprise an elastomer.
Layers exhibiting high temperature resistance may include, for example, prepolymers such as silicone, polytetrafluoroethylene, polythioethers, polysulfides, polyformals, polybutadiene, certain elastomers, and combinations of any of the foregoing; or a composition having a high crosslink density.
Layers exhibiting high tensile strength may include, for example, elastomeric prepolymers such as silicone and polybutadiene, compositions having high crosslink densities, inorganic fillers, and combinations of any of the foregoing.
Layers exhibiting high% elongation may include, for example, elastomeric prepolymers such as silicone and polybutadiene, compositions having high crosslink densities, inorganic fillers, and combinations of any of the foregoing.
The layer exhibiting substrate adhesion or adhesion to the primer coating may include, for example, an adhesion promoter such as an organofunctional alkoxysilane, a phenolic resin, and combinations of any of the foregoing, titanates, partially hydrolyzed alkoxysilanes, or combinations thereof.
The layer exhibiting interlayer adhesion may include, for example, adhesion promoters, unreacted functional groups that can react with compounds in adjacent layers, and combinations thereof.
The layer exhibiting a fast tack free time may include, for example, co-reactants having a fast cure chemistry, a system curable by actinic radiation, a catalyst, and combinations of any of the foregoing.
The layer exhibiting a fast shore 10A hardness time may include, for example, co-reactants having a fast cure chemistry, a system curable by actinic radiation, a catalyst, and combinations of any of the foregoing.
The layer exhibiting electrical conductivity, EMI/RFI shielding and/or static dissipation may comprise, for example, a conductive filler or a combination of conductive fillers.
The layer exhibiting low density may comprise, for example, a low density filler such as a low density organic filler, hollow microspheres, coated microspheres, or a combination of any of the foregoing.
The layer exhibiting corrosion resistance may include, for example, one or more corrosion inhibitors.
The layer exhibiting corrosion resistance may include, for example, one or more inorganic fillers.
The method of the present invention uses co-reactive three-dimensional printing to manufacture the sealing cap or portions of the sealing cap. Coreactive three-dimensional printing refers to an automated manufacturing process in which a coreactive composition is extruded through a nozzle and deposited using automated control. In co-reactive three-dimensional printing, a one-part co-reactive composition may be pumped into the three-dimensional printing apparatus and the curing reaction may be initiated by application of energy, for example by exposing the co-reactive composition to UV radiation. Alternatively, at least two coreactive components may be combined and mixed to form a coreactive composition, which may then be extruded through a nozzle and deposited.
A three-dimensional printing apparatus for manufacturing a part may include one or more pumps, one or more mixers, and one or more nozzles. One or more co-reactive compositions may be pumped into one or more mixers and forced under pressure through one or more nozzles, directed onto a surface or previously applied layer.
The three-dimensional printing device may include, for example, a pressure control, an extrusion die, a coextrusion die, a coating applicator, a temperature control element, an element for applying energy to the coreactive composition, or a combination of any of the foregoing.
The three-dimensional printing device may comprise a build device for moving the nozzle in three dimensions relative to the surface. The movement of the three-dimensional printing device may be controlled by a processor.
Any suitable co-reactive three-dimensional printing device may be used to deposit the co-reactive composition. The selection of a suitable co-reactive three-dimensional printing device may depend on a number of factors including the deposition volume, viscosity of the co-reactive composition, deposition rate, reaction rate of the co-reactive compound, and complexity and size of the chemical resistant portion being manufactured. Each of the two or more co-reactive components may be introduced into a separate pump and injected into a mixer to combine and mix the two co-reactive components to form a co-reactive composition. The nozzle may be coupled to a mixer and the mixed co-reactive composition may be forced under pressure or extruded through the nozzle.
The pump may be, for example, a positive displacement pump, a syringe pump, a piston pump, or a progressive cavity pump. The two pumps delivering the two coreactive components may be placed in parallel or in series. A suitable pump may be capable of pushing liquid or viscous liquid through the nozzle orifice. This process may also be referred to as extrusion. The co-reactive components may also be introduced into the mixer using two pumps in series.
For example, two or more co-reactive components may be deposited by dispensing material through a disposable nozzle attached to a progressive cavity two-component system in which the co-reactive components are mixed in-line. The two-component system may comprise, for example, two progressive cavity pumps that respectively give the co-reactive components into a disposable static mixer dispenser or dynamic mixer. Other suitable pumps include positive displacement pumps, syringe pumps, piston pumps, and progressive cavity pumps. After mixing to form the co-reactive composition, the co-reactive composition is forced under pressure through one or more dies and/or one or more nozzles to form an extrudate for deposition onto the base to provide an initial layer of chemical resistant moieties, and a continuous layer may be deposited on and/or adjacent to the previously deposited layer. The deposition system may be positioned orthogonal to the base, but may be disposed at any suitable angle to form the extrudate such that the extrudate and the deposition system form an obtuse angle, with the extrudate being parallel to the base. Extrudate refers to the co-reactive composition after the co-reactive components are mixed, for example, in a static mixer or a dynamic mixer. The extrudate may be shaped as it passes through a die and/or nozzle.
The base, the deposition system, or both the base and the deposition system may be hinged to build a three-dimensional chemical resistant part. The movement may be performed in a predetermined manner, which may be accomplished using any suitable CAD/CAM method and device such as a robotic and/or computerized machine interface.
The extrudate formed by extruding the co-reactive composition through the nozzle of the three-dimensional printing device may be deposited in any orientation. For example, the nozzles may be oriented downward, upward, sideways, or at any angle therebetween. In this way, the co-reactive composition may be deposited as a vertical wall or as a overhang. The extrudate may be deposited on the bottom of the vertical wall, the lower surface of the inclined wall, or the horizontal surface. The use of extrudates with fast curing chemistry may facilitate the deposition of an upper layer adjacent to a lower layer such that an angled surface may be fabricated. The angled surface may be inclined upwardly relative to the horizontal or downwardly relative to the horizontal.
The extrudate may be dispensed continuously or intermittently to form an initial layer and a continuous layer. For intermittent deposition, the deposition system may interface with a switch to shut off a pump, such as a progressive cavity pump, and thereby interrupt the flow of the co-reactive composition.
The three-dimensional printing system may include an in-line static and/or dynamic mixer and a separate pressurized pumping compartment to contain and supply at least two co-reactive components into the static and/or dynamic mixer. Mixers such as active mixers may include a variable speed center impeller with high shear blades within the nozzle. A series of nozzles having a minimum size of, for example, 0.2mm to 100mm, 0.5mm to 75mm, 1mm to 50mm, or 5mm to 25mm may be used. The nozzle may have a minimum size of, for example, greater than 1mm, greater than 2mm, greater than 5mm, greater than 10mm, greater than 20mm, greater than 30mm, greater than 40mm, greater than 50mm, greater than 60mm, greater than 70mm, greater than 80mm, or greater than 90 mm. The nozzle may have a minimum size of, for example, less than 100mm, less than 90mm, less than 80mm, less than 70mm, less than 60mm, less than 50mm, less than 40mm, less than 30mm, less than 20mm, less than 10mm, or less than 5 mm. The nozzle may have any suitable cross-sectional dimension, such as, for example, circular, spherical, oval, rectangular, square, trapezoidal, triangular, planar, or other suitable shape. The ratio of the aspect ratio or orthogonal dimensions may be any suitable dimension suitable for manufacturing the chemical resistant portion, such as 1:1, greater than 1:2, greater than 1:3, greater than 1:5, or greater than 1:10.
A series of static and/or dynamic mixing nozzles may be used having an outlet aperture size of, for example, 0.6mm to 2.5mm and a length of 30mm to 150 mm. For example, the outlet aperture diameter may be 0.2mm to 4.0mm, 0.4mm to 3.0mm, 0.6mm to 2.5mm, 0.8mm to 2mm, or 1.0mm to 1.6mm. The static mixer and/or the dynamic mixer may have a length of, for example, 10mm to 200mm, 20mm to 175mm, 30mm to 150mm, or 50mm to 100 mm. The mixing nozzle may include a static and/or dynamic mixing section and a dispensing section coupled to the static and/or dynamic mixing section. The static and/or dynamic mixing section may be configured to combine and mix co-reactive materials. The distribution section may be, for example, a straight tube having any of the above-mentioned hole diameters. The length of the dispensing section may be configured to provide a region in which the co-reactive components may begin to react and increase viscosity prior to deposition on the article. For example, the length of the dispense section may be selected based on the deposition rate, the reaction rate of the coreactants, and the viscosity of the coreactant composition.
The co-reactive composition may have a residence time in the static and/or dynamic mixing nozzle of, for example, 0.25 seconds to 5 seconds, 0.3 seconds to 4 seconds, 0.5 seconds to 3 seconds, or 1 second to 3 seconds. Other residence times may be suitably used based on the cure chemistry and cure rate.
Typically, suitable residence times are less than the gel time of the co-reactive composition.
The co-reactive composition may have a volumetric flow rate of, for example, 0.1 mL/min to 20,000 mL/min, such as 1 mL/min to 12,000 mL/min, 5 mL/min to 8,000 mL/min, or 10 mL/min to 6,000 mL/min. The volumetric flow rate may depend on, for example, the viscosity of the co-reactive composition, the extrusion pressure, the nozzle diameter, and the reaction rate of the co-reactive compound.
The co-reactive composition may be applied at a deposition rate of, for example, 1 mm/sec to 400 mm/sec, for example, 5 mm/sec to 300 mm/sec, 10 mm/sec to 200 mm/sec, or 15 mm/sec to 150 mm/sec. The deposition rate may depend on, for example, the viscosity of the co-reactive composition, the extrusion pressure, the nozzle diameter, and the reaction rate of the co-reactive compound. Deposition rate refers to the rate at which the nozzle used to extrude the co-reactive composition is moved relative to the surface on which the co-reactive composition is deposited.
The static and/or dynamic mixing nozzles may be heated or cooled to control, for example, the reaction rate between the co-reactive compounds and/or the viscosity of the co-reactive components. The apertures of the deposition nozzle may have any suitable shape and size. The system may include a plurality of deposition nozzles. The nozzle may have a fixed orifice size and shape, or the nozzle orifice may be controllably adjustable. The mixer and/or nozzle may be cooled to control the exotherm generated by the reaction of the co-reactive compounds.
The rate at which the co-reactive composition reacts to form the thermoset polymeric matrix may be determined and/or controlled by the choice of reactive functional groups of the co-reactive compound. The reaction rate may also be determined by factors that reduce the activation energy of the reaction, such as heat and/or catalysts.
The reaction rate may be reflected in the gel time of the coreactive composition. Fast cure chemistry refers to chemistry wherein the gel time of the co-reactive compound is, for example, less than 30 minutes, less than 20 minutes, less than 10 minutes, less than 5 minutes, less than 4 minutes, less than 3 minutes, less than 2 minutes, less than 1 minute, less than 45 seconds, less than 30 seconds, less than 15 seconds, or less than 5 seconds. The coreactive composition may have a gel time of, for example, 0.1 seconds to 5 minutes, 0.2 seconds to 3 minutes, 0.5 seconds to 2 minutes, 1 second to 1 minute, or 2 seconds to 40 seconds. Gel time is the time that the co-reactive composition can no longer be stirred by hand after mixing the co-reactive components. The gel time of the latent coreactive composition refers to the time from the first initiation of the curing reaction to the inability to agitate the coreactive composition by hand.
The size of the co-reactive composition and the extrudate forced through the nozzle is not particularly limited, as the co-reactive components can be uniformly combined and mixed and the co-reactive composition can begin to cure immediately after mixing. Thus, co-reactive additive manufacturing facilitates the use of large-sized extrudates, which facilitates the ability to quickly manufacture small and large sealing caps.
Using the co-reactive three-dimensional printing method, the co-reactive composition may be deposited, for example, at a rate of 1 mm/sec to 400 mm/sec and/or at a flow rate of 0.1 mL/min to 20,000 mL/min.
The sealing cap and the layer of the sealing cap containing the sealing cap shell may have a visually smooth surface. Photographs of the sealing cap are shown in fig. 3A-3B, which illustrate the sealing cap with a gradually smoother surface (from fig. 3A to 3C) achieved by reducing the thickness of the print layer. Fig. 3D shows confocal laser scanning microscopy surface profiles at 10X magnification of the outer surface of the corresponding sealing cap shown in fig. 3A-3C. The seal cap and seal cap surface shown in fig. 3A-3D are made using a polyurea coreactive composition formed by combining a polyamine component and a polyisocyanate component.
The sealing cap may have properties suitable for the particular application. Related properties include chemical resistance, low temperature flexibility, hydrolytic stability, high temperature resistance, tensile strength, elongation, substrate adhesion, adhesion to adjacent sealant layers, tack free time, shore 10A hardness time, electrical conductivity, static dissipation, thermal conductivity, low density, corrosion resistance, surface hardness, flame retardancy, UV resistance, rain erosion resistance, dielectric breakdown strength, and combinations of any of the foregoing.
For aerospace applications, properties may include chemical resistance, such as resistance to fuels, hydraulic fluids, oils, fats, lubricants, and solvents, low temperature flexibility, high temperature resistance, ability to dissipate electrical charges, and/or dielectric breakdown strength. When fully cured, the sealing cap may be visually transparent to facilitate visual inspection of the interface between the fastener and the sealant.
When fully cured, the shell and the interior volume comprising the cured second coreactive composition may exhibit one or more different properties. For example, the shell may exhibit chemical resistance, electrical conductivity, hydrolytic stability, high dielectric breakdown strength, or a combination of any of the foregoing. For example, the second co-reactive composition, when cured, may exhibit adhesion to fasteners, chemical resistance, low density, high tensile strength, high% elongation, or a combination of any of the foregoing.
The percentage of volume expansion of the seal cap after immersion in JRF type I at 140°f (60 ℃) and ambient pressure is no greater than 40%, in some cases no greater than 25%, in some cases no greater than 20%, and in other cases no greater than 10%, according to methods similar to those described in ASTM D792 (american society for testing and materials) or AMS 3269 (aerospace materials specification). JRF type I, for determining fuel resistance, has the following composition: toluene: 28+ -1% by volume; cyclohexane (industrial): 34±1% by volume; isooctane: 38+ -1% by volume; and t-dibutyl disulfide: 1.+ -. 0.005% by volume (see AMS2629, release 7.1.1989, +.3.1.1, etc. available from SAE (society of automotive Engineers)).
After exposure to a jet reference fluid (JRF type 1) at 60 ℃ for 168 hours according to ISO 1817, the provided cured composition may exhibit a tensile strength of greater than 1.4MPa determined according to ISO 37, a tensile elongation of greater than 150% determined according to ISO 37, and a hardness of greater than shore 30A determined according to ISO 868, wherein the test is performed at a temperature of 23 ℃ and a humidity of 55% RH.
After exposure to deicing fluid at 60 ℃ for 168 hours according to ISO 11075 1, the cured composition may exhibit a tensile strength of greater than 1MPa determined according to ISO 37 and a tensile elongation of greater than 150% determined according to ISO 37, wherein the test is conducted at a temperature of 23 ℃ and a humidity of 55% RH.
Exposure to phosphate hydraulic fluid at 70 cLD-4) after 1,000 hours, the cured composition may exhibit a tensile strength of greater than 1MPa as determined according to ISO 37, a tensile elongation of greater than 150% as determined according to ISO 37 and a hardness of greater than Shore 30A as determined according to ISO 868, wherein the test is conducted at a temperature of 23 ℃ and a humidity of 55% RH. After 7 days of immersion in the chemical at 70 ℃, the chemical resistant composition may exhibit less than 25%Less than 20%, less than 15% or less than 10% swelling, wherein% swelling is determined according to EN ISO 10563.
The sealing cap may exhibit a hardness of, for example, greater than shore 20A, greater than shore 30A, greater than shore 40A, greater than shore 50A, or greater than shore 60A, wherein the hardness is determined according to ISO 868 at 23 ℃/55% RH.
The sealing cap may exhibit a tensile elongation of at least 200% and a tensile strength of at least 200psi when measured according to the procedure described in AMS 3279, ≡ 3.3.17.1, test procedure AS5127/1, ≡7.7.
The overlap shear strength of the seal cap may be greater than 200psi (1.38 MPa), such AS at least 220psi (1.52 MPa), at least 250psi (1.72 MPa), and in some cases at least 400psi (2.76 MPa), when measured according to the procedure described in SAE AS5127/1 paragraph 7.8.
The sealing caps prepared from the co-reactive compositions provided by the present disclosure may meet or exceed the requirements of the aerospace sealants set forth in AMS 3277.
The conductive sealing caps or layers of sealing caps provided by the present disclosure may exhibit, for example, less than 10 6 Ohm/square, less than 10 5 Ohm/square, less than 10 4 Ohm/square, less than 10 3 Ohm/square, less than 10 2 Ohm/square, less than 10 -1 Ohm/square or less than 10 -2 Surface resistivity in ohm/square. The surface of the conductive sealing cap or layer of the sealing cap provided by the present disclosure may have, for example, 10 -2 To 10 2 、10 2 Ohm/square to 10 6 Ohm/square or 10 3 Ohm/square to 10 5 Surface resistivity in ohm/square. The surface resistivity may be determined according to ASTM D257 at 23 ℃/55% rh.
The sealing cap or layer of the sealing cap provided by the present disclosure may have, for example, less than 10 6 Ohm/cm, less than 10 5 Ohm/cm, less than 10 4 Ohm/cm, less than 10 3 Ohm/cm, less than 10 2 Ohm/cm, less than 10 -1 Ohm/cm or less than 10 -2 Ohm/cmVolume resistivity. The conductive sealing cap or the layer of the sealing cap may have, for example, 10 -2 Ohm/cm to 10 1 Ohm/cm, 10 2 Ohm/cm to 10 6 Ohm/cm or 10 3 Ohm/cm to 10 5 Volume resistivity in ohm/cm. The volume resistivity may be determined at 23 ℃/55% RH according to ASTM D257.
The sealing cap or layer of sealing cap provided by the present disclosure may have, for example, greater than 1S cm -1 More than 10S cm -1 More than 100S cm -1 More than 1,000S cm -1 Or greater than 10,000S cm -1 Is a high-conductivity metal. The conductive sealing cap may have a thickness of 1S cm -1 To 10,000S cm -1 、10S cm -1 To 1,000S cm -1 Or 10S cm -1 To 500S cm -1 Is a high-conductivity metal.
The sealing cap or layer of sealing caps provided by the present disclosure may exhibit an attenuation of, for example, greater than 10dB, greater than 30dB, greater than 60dB, greater than 90dB, or greater than 120dB at frequencies in the range of 10KHz to 20 GHz. The conductive sealing caps provided by the present disclosure may exhibit, for example, 10dB to 120dB, 20dB to 100dB, 30dB to 90dB, or 40dB to 70dB of attenuation at frequencies in the range of 10KHz to 20 GHz.
The seal cap or layer of the seal cap provided by the present disclosure exhibits a thermal conductivity of 0.1 to 50W/(m-K), 0.5 to 30W/(m-K), 1 to 20W/(m-K), 1 to 10W/(m-K), 1 to 5W/(m-K), 2 to 25W/(m-K), or 5 to 25W/(m-K).
The sealing cap or layer of sealing cap provided by the present disclosure may exhibit a specific gravity of, for example, less than 1.1, less than 1.0, less than 0.9, less than 0.8, or less than 0.7, wherein the specific gravity is determined according to ISO 2781 at 23 ℃/55% RH.
The co-reactive three-dimensional printing method provided by the present disclosure can be used to manufacture sealing caps with high mechanical strength of adjacent layers. Adjacent layers of the coreactive composition may be chemically bonded and/or physically bonded to create an interlayer interface of high mechanical strength. The strength of the interlayer interface can be determined by measuring the fracture energy according to ASTM D7313. The sealing caps made using the methods provided by the present disclosure may have a fracture energy substantially the same as the fracture energy of the individual layers. For example, the fracture energy of the sealing cap and the fracture energy of the individual cured layers of the coreactive composition may be within, for example, less than 10%, less than 5%, less than 2%, or less than 1%.
The sealing cap provided by the present disclosure may be used to seal a fastener. Examples of fasteners include anchors, cap screws, cotter pins, eyebolts, nuts, rivets, self-locking fasteners, self-tapping screws, sleeves, tapping screws, tum and thumb screws, welding screws, bending bolts, fixed panel fasteners, machine screws, retaining rings, screwdriver bits, self-drilling screws, self-expanding metal brackets, spring nuts, thread rolling screws, and washers.
The fastener may be a fastener on a surface of a vehicle, including, for example, an automobile, an aerospace vehicle, an automobile, a truck, a bus, a van, a motorcycle, a scooter, a recreational vehicle; rail vehicles trains, trams, bicycles, airplanes, rockets, spacecraft, jet planes, helicopters, military vehicles, including jeep, transportation vehicles, combat support vehicles, weapons, infantry combat vehicles, lightning protection vehicles, light armored vehicles, light utility vehicles, military trucks, water vehicles, including ships, boats, and recreational boats. The term "vehicle" is used in its broadest sense and encompasses all types of aircraft, spacecraft, watercraft and land vehicles. For example, the vehicle may comprise an aircraft, such as an airplane, including a private aircraft; small, medium or large commercial airliners, cargo aircraft and military aircraft; helicopters, including private, commercial and military helicopters; aerospace vehicles, including rockets and other spacecraft. The vehicle may comprise a ground vehicle such as, for example, a trailer, a car, a truck, a bus, a van, an engineering vehicle, a golf cart, a motorcycle, a bicycle, a train, and a railroad car. The vehicle also comprises an on-water tool such as, for example, a ship, a boat, and a gasketed boat.
The fastener may be a fastener on a surface of an aerospace vehicle. Examples of aerospace vehicles include F/A-18 jet aircraft or related aircraft, such as F/A-18E super hornets and F/A-18F; boeing 787dream airliners (787 streamliner), 737, 747, 717 jet airliners, and related aircraft (produced by boeing commercial aircraft company (Boeing Commercial Airplanes); v-22Osprey tiltrotor aircraft (V-22 Osprey); VH-92, S-92 and related aircraft (manufactured by naval aviation systems commander (navai) and scoos aircraft company (Sikorsky)); g650, G600, G550, G500, G450 and related aircraft (produced by Gulfstream); and a350, a320, a330 and related aircraft (manufactured by Airbus corporation (Airbus)). The sealing cap may be used in any suitable commercial, military or general aviation aircraft, such as, for example, aircraft produced by pombardi (combard inc.) and/or pombardi (Bombardier Aerospace), such as canadian area airlines (Canadair Regional Jet, CRJ) and related aircraft; an aircraft produced by Rockweld Martin (Lockheed Martin), such as an F-22 bird fighter (F-22 Raptor), an F-35Lightning fighter (F-35 Lightning), and related aircraft; aircraft produced by Northrop grid Lu Man (Northrop Grumman), such as the B-2 ghost strategic bomber (B-2 Spirit) and related aircraft; an Aircraft manufactured by Pi Latu s Aircraft limited (Pilatus air ltd.); an aircraft produced by a daily airline company (Eclipse Aviation Corporation); or an Aircraft manufactured by the japanese aerospace company (Eclipse Aerospace, kestrel Aircraft company (Kestrel airft)).
The fastener may be a fastener on a fuel container, such as a fuel tank of an aerospace vehicle.
The fastener may be one that is protected from exposure to solvents such as fuel and/or hydraulic fluid under conditions of use.
Vehicles such as automotive and aerospace vehicles that include fasteners sealed using the methods provided by the present disclosure are also within the scope of the present invention.
Aspects of the invention
The invention may be further defined by one or more of the following aspects.
Aspect 1. A method of sealing a fastener includes depositing a continuous layer comprising a first co-reactive composition directly onto the fastener by three-dimensional printing.
Aspect 2. The method of aspect 1, wherein the continuous layer is deposited to form a sealing cap.
Aspect 3 the method according to any one of aspects 1 and 2, further comprising: depositing a second co-reactive composition directly onto the first co-reactive composition; or simultaneously depositing successive layers of the first and second co-reactive compositions onto the fastener.
Aspect 4 the method of any one of aspects 1 to 3, further comprising applying a sealing cap over the outermost deposited first co-reactive composition, wherein the sealing cap comprises an at least partially cured second co-reactive composition; and the second co-reactive composition is the same as or different from the outermost deposited co-reactive composition.
Aspect 5 the method of any one of aspects 1 and 2, further comprising depositing a continuous layer of a second co-reactive composition by three-dimensional printing to form the sealing cap over the first co-reactive composition.
Aspect 6. A method of manufacturing a sealing cap, comprising: depositing successive layers of a first co-reactive composition by three-dimensional printing to form a sealed cap shell defining an interior volume; and filling the interior volume with a second co-reactive composition to provide a sealing cap.
Aspect 7. The method of aspect 6, wherein filling the interior volume comprises depositing the second co-reactive composition using three-dimensional printing.
Aspect 8 the method of any one of aspects 4 to 7, wherein the sealing cap is dome-shaped having a base width of 5mm to 50mm, preferably 10mm to 40 mm; a height of 5mm to 50mm, preferably 20mm to 40 mm; and an average wall thickness of 0.5mm to 25mm, preferably 1mm to 20mm, 1.5mm to 15mm or 2mm to 10 mm.
Aspect 9 the method of any one of aspects 3 to 8, wherein the first co-reactive composition is reactive with the second co-reactive composition.
Aspect 10 the method of any one of aspects 3 to 9, wherein the second co-reactive composition is the same as the first co-reactive composition.
Aspect 11 the method of any one of aspects 3 to 9, wherein the second co-reactive composition is different from the first co-reactive composition.
Aspect 12 the method of any one of aspects 6-11, further comprising at least partially curing the sealing cap shell after forming the shell and before filling the interior volume.
Aspect 13 the method of any one of aspects 3 to 12, wherein each of the first and second co-reactive compositions independently comprises a sulfur-containing prepolymer.
Aspect 14. The method of aspect 13, wherein each of the first and second co-reactive compositions independently comprises 40wt% to 80wt% of the sulfur-containing prepolymer.
Aspect 15 the method of any one of aspects 13 to 14, wherein the sulfur-containing prepolymer has a sulfur content of greater than 10wt%, wherein wt% is based on the total weight of the sulfur-containing prepolymer.
Aspect 16 the method of any one of aspects 13 to 14, wherein the sulfur-containing prepolymer comprises a polythioether, a polysulfide, a sulfur-containing polyformal, a monosulfide, or a combination of any of the foregoing.
Aspect 17 the method of any one of aspects 3 to 16, wherein each of the first and second co-reactive compositions independently comprises an actinic radiation curable co-reactive composition; and the method further comprises exposing the first co-reactive composition and/or the second co-reactive composition to actinic radiation prior to depositing the first co-reactive composition and/or the second co-reactive composition, while depositing the first co-reactive composition and/or the second co-reactive composition, and/or after depositing the first co-reactive composition and/or the second co-reactive composition.
Aspect 18 the method of any one of aspects 1 to 16, wherein the first coreactive composition is curable upon exposure to actinic radiation.
Aspect 19 the method of any one of aspects 3 to 16, wherein the first coreactive composition is non-curable upon exposure to actinic radiation.
Aspect 20. A sealing cap manufactured using the method according to any one of aspects 1 to 19.
Aspect 21. The sealing cap of aspect 20, wherein the breaking energy of the fully cured sealing cap is substantially the same as the breaking energy of the individual layers forming the sealing cap, wherein the breaking energy is determined according to ASTM D7313.
Aspect 22. A sealing cap manufactured using the method of any one of aspects 3 to 19, wherein a layer prepared from the first co-reactive composition is chemically and/or physically bonded to a layer prepared from the second co-reactive composition.
Aspect 23. A method of sealing a fastener comprising applying the sealing cap of any one of aspects 20 to 22 over a fastener and allowing the first and/or second co-reactive compositions to cure.
Aspect 24. A fastener sealed with the sealing cap according to any one of aspects 20 to 22
Aspect 25 the fastener of aspect 24, wherein the fastener is on a vehicle such as an aerospace vehicle.
Examples
Embodiments provided by the present disclosure are further described by reference to the following examples, which describe methods of sealing fasteners and methods of manufacturing sealing caps using three-dimensional printing. It will be apparent to those skilled in the art that many modifications, both to materials and methods, may be practiced without departing from the scope of the disclosure.
Example 1
UV curing sealing cap
One-part fuel resistant sealant formulation PR 2001B 2 Aerospace sealants available from PPG Aerospace comprise a combination of a thiol-terminated polythioether prepolymer, a divinyl ether monomer, a rheology modifier, a filler, and a photoinitiator. The formulation was stored in UV opaque tubes at-40 ℃ and thawed to room temperature (25 ℃) prior to use. The sealant formulation was introduced into a three-dimensional printing system consisting of a LulzBot Taz 3D printing gantry and a printing bed integrated with a ViscoTec Eco-Duo twin extruder. UV Source [ (] WF-501B UV LED flashlight, peak wavelength 395 nm) was mounted on a ViscoTec extruder and directed from the extruder to the point of application 5.5cm from the print bed.
The fuel resistant sealant formulation was loaded into an opaque Nordson box that was connected to a ViscoTec extruder using a PTFE tube that was shielded from ambient light. The loaded cartridge was pressurized to 80psi under nitrogen and printed using a custom written G code, which simultaneously led the printhead and the print bed and simultaneously switched the formulation flow through the ViscoTec unit. The fuel resistant sealant formulation was extruded through a static mixing nozzle with an inner diameter of 0.6mm onto the print bed. The sealing cap was constructed by depositing a continuous spiral of sealant using a printhead speed of 120 mm/sec and a flow rate of 1.2 mL/min. Under these conditions, the extruded sealant formulation had a G "of about 8E4 and a G 'of 1E5 at 3 hours after activation and a G" of 3E5 and a G' of 8.5E5 at 6 hours after activation. Shear storage modulus G 'and shear loss modulus G' were measured using an Anton Paar MCR 302 rheometer with a gap set at 1mm, parallel plate axis diameter at 2mm, oscillation frequency at 1Hz, amplitude at 0.3%, and plate temperature at 25 ℃. The sealing cap is modeled as a dome-like structure using 3D modeling software. The bottom of the sealing cap had a diameter of 42.4mm and a height of 39.9mm.
Example 2
Seal cap manufactured using thiol/epoxy chemistry
The co-reactive composition was prepared by combining a first component and a second component based on PR-2001B1/2 (a two-part thiol/epoxy Aerospace sealant available from PPG Aerospace).
The first component PR-2001B1/2 part B comprises a thiol-terminated polythioether prepolymer, an epoxy-functional alkoxysilane adhesion promoter, and a partially hydrogenated tetrabiphenyl and higher order polybiphenyl. Weigh the first component into a Max 300LDAC cup (FlackTek) and use standardThe procedure was deaerated.
The second component PR-2001B1/2 part A comprises bisphenol-A- (epichlorohydrin); an epoxy resin. The second component was weighed into a Max 300L DAC cup (FlackTek) and standard was usedThe procedure was deaerated.
Using FlackTekTransfer of degassed component from DAC cup to +.>In the cartridge, and the coreactive composition is formed by mixing the two components in a weight ratio of 100:18.5. The co-reactive composition was printed using a ViscoTec 2K extruder mounted to a Lulzbot Taz 6 gantry.
A continuous layer of the co-reactive composition is deposited to build up a sealed cap.
Example 3
2 Sealing cap made using MnO catalyzed polysulfide chemistry
The co-reactive composition was prepared by combining a first co-reactive component and a second co-reactive component based on PR-1429B2 (a two-part Mn dioxide cured polysulfide Aerospace sealant available from PPG Aerospace).
The first co-reactive component PR-1429B2 part B comprises a thiol-terminated polysulfide prepolymer. Weigh the first coreactive component into a Max300L DAC cup (FlackTek) and use standardThe procedure was deaerated.
The second coreactive component PR-1429B2 part A comprises MnO 2 A catalyst. The second component was weighed into a Max300L DAC cup (FlackTek) and standard was usedThe procedure was deaerated.
Using FlackTekThe degassed co-reactive components were transferred from the DAC cup into an Optimum cartridge and the co-reactive composition formed by mixing the two components in a weight ratio of 100:10 was printed using a ViscoTec 2K extruder mounted onto a Lulzbot Taz 6 gantry.
A continuous layer of the co-reactive composition is deposited to build up a sealed cap.
Example 4
UV-cured polythioether sealing cap
Aerospace seal caps are 3D printed using an actinic radiation curable thiol-ene resin formulation.
The thiol-ene formulation comprises a mixture of thiol-and alkenyl-terminated resins, a rheology modifier, a filler, and a photoinitiator. The formulation was stored in UV opaque tubes at-40 ℃ and thawed to 23 ℃ prior to use. Thiol-ene formulations were 3D printed using a custom 3D printer that was 3D printed gantry and ViscoTec by LulzBot Taz Integrated printing bed group of Eco-DUO double extruderAnd (3) forming the finished product. UV Source (+)>WF-501B UV LED torch, nominal peak wavelength 395 nm) was mounted on a ViscoTec extruder and directed from the extruder to the point of application 5.5cm from the print bed.
Thiol and alkenyl components were loaded into opaque Nordson cartridges that were connected to a ViscoTec extruder using polytetrafluoroethylene tubing wrapped with aluminum foil to prevent ambient light penetration. The loaded cartridge was pressurized to 80psi (0.551N/mm under nitrogen 2 ) And printing using a custom written G-code, which simultaneously directs the printhead and the print bed and simultaneously switches the flow of the co-reactive composition formed by mixing the thiol and alkenyl components through the ViscoTec extruder.
After the extrusion was initiated, the UV LED lamp was turned on. The liquid thiol-ene formulation was extruded through a static mixing nozzle with an inner diameter of 0.6mm onto a print bed. The sealing caps were printed in a continuous spiral pattern using a printhead speed of 120 mm/sec and a flow rate of 1.2 mL/min. Under these conditions, the extruded co-reactive composition cured within 5 seconds after exiting the extruder.
In the present example, autodesk Inventor is used2019 model the sealing cap as a dome-shaped structure. The bottom of the sealing cap had a diameter of 42.36mm and a height of 39.89mm. Three-dimensional printing of the sealing caps cured under these conditions required 9.6 minutes.
A photograph of the three-dimensionally printed sealing cap is shown in fig. 4.
Finally, it should be noted that there are alternative ways of implementing the embodiments disclosed herein. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive. Furthermore, the claims are not to be limited to the details given herein and are entitled to their full scope and equivalents.

Claims (25)

1. A sealing fastener manufactured by a method comprising depositing successive layers comprising a first co-reactive composition directly onto the fastener by three-dimensional printing.
2. The sealing fastener of claim 1 wherein said continuous layer is deposited to form a sealing cap.
3. The sealing fastener of any one of claims 1 and 2, further comprising:
depositing a second co-reactive composition directly onto the first co-reactive composition.
4. The sealing fastener of any of claims 1 to 3 further comprising applying a sealing cap shell onto the outermost deposited first co-reactive composition, wherein
The sealing cap comprises an at least partially cured second co-reactive composition; and is also provided with
The second co-reactive composition is the same as or different from the outermost deposited co-reactive composition.
5. The sealing fastener of any one of claims 1 and 2, further comprising depositing a continuous layer of a second co-reactive composition by three-dimensional printing to form the sealing cap over the first co-reactive composition.
6. A sealing fastener having a sealing cap over the fastener, the sealing cap being manufactured by a method comprising:
depositing successive layers of a first co-reactive composition by three-dimensional printing to form a sealed cap shell defining an interior volume; and
filling the internal volume with a second co-reactive composition to provide a sealing cap.
7. The sealing fastener of claim 6, wherein filling the interior volume comprises depositing the second co-reactive composition using three-dimensional printing.
8. The sealing fastener of any of claims 4 to 7, wherein the sealing cap is dome-shaped having a base width of 5mm to 50mm, preferably 10mm to 40 mm; a height of 5mm to 50mm, preferably 20mm to 40 mm; and an average wall thickness of 0.5mm to 25mm, preferably 1mm to 20mm, 1.5mm to 15mm or 2mm to 10 mm.
9. The sealing fastener of any of claims 3-8 wherein the first co-reactive composition is reactive with the second co-reactive composition.
10. The sealing fastener of any one of claims 3 to 9, wherein the second co-reactive composition is the same as the first co-reactive composition.
11. The sealing fastener of any of claims 3-9, wherein the second co-reactive composition is different from the first co-reactive composition.
12. The sealing fastener of any of claims 6-11, further comprising at least partially curing the sealing cap shell after forming the shell and before filling the interior volume.
13. The sealing fastener of any one of claims 1 to 12 wherein each of the first and second co-reactive compositions independently comprises a sulfur-containing prepolymer.
14. The sealing fastener of claim 13, wherein each of the first and second co-reactive compositions independently comprises 40wt% to 80wt% of the sulfur-containing prepolymer.
15. The sealing fastener of any one of claims 13 to 14 wherein the sulfur-containing prepolymer has a sulfur content of greater than 10wt%, wherein wt% is based on the total weight of the sulfur-containing prepolymer.
16. The sealing fastener of any of claims 13 to 14, wherein the sulfur-containing prepolymer comprises a polythioether, a polysulfide, a sulfur-containing polyformal, a monosulfide, or a combination of any of the foregoing.
17. The sealing fastener of any one of claims 3 to 16, wherein
Each of the first and second coreactive compositions independently comprises an actinic radiation curable coreactive composition; and is also provided with
The method further comprises exposing the first co-reactive composition and/or the second co-reactive composition to actinic radiation prior to depositing the first co-reactive composition and/or the second co-reactive composition, while depositing the first co-reactive composition and/or the second co-reactive composition, and/or after depositing the first co-reactive composition and/or the second co-reactive composition.
18. The sealing fastener of any one of claims 1 to 16 wherein the first co-reactive composition is curable upon exposure to actinic radiation.
19. The sealing fastener of any of claims 3 to 16 wherein the first co-reactive composition is non-curable upon exposure to actinic radiation.
20. The sealing fastener of any of claims 2 to 19, wherein the breaking energy of the fully cured sealing cap is substantially the same as the breaking energy of the individual layers forming the sealing cap, wherein the breaking energy is determined according to ASTM D7313.
21. The sealing fastener of any of claims 3-19 wherein a layer prepared from the first co-reactive composition is chemically and/or physically bonded to a layer prepared from the second co-reactive composition.
22. The sealing fastener of any one of claims 1 to 21, wherein the fastener is on a vehicle such as an aerospace vehicle.
23. The sealing fastener of any of claims 1 to 21, wherein the sealing cap has an outer layer forming a shell (102) and an inner layer (103) surrounding a fastener (104) mounted to a surface (105).
24. The sealing fastener of any of claims 1 to 21, wherein the sealing cap has a single layer (106) surrounding the fastener (104) mounted to the surface (105).
25. A method of sealing a fastener comprising applying a sealing cap made in accordance with the method of any one of claims 1 to 24 over a fastener and allowing the first co-reactive composition and/or the second co-reactive composition to cure.
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